On 5 December 1991, Williams was elected Bishop of Monmouth in the Church in Wales: he was consecrated a bishop on 1 May 1992 at St Asaph Cathedral and enthroned at Newport Cathedral on 14 May. He continued to serve as Bishop of Monmouth after he was elected to also be the Archbishop of Wales in December 1999, in which capacity he was enthroned again at Newport Cathedral on 26 February 2000.

In 2002, he was announced as the successor to George Carey as Archbishop of Canterbury — the senior bishop in the Church of England.
The Archbishop of Canterbury in England acts as a focus of unity recognised as primus inter pares ("first among equals") but does not exercise authority in Anglican provinces outside the Church of England.
As a bishop of the disestablished Church in Wales, Williams was the first Archbishop of Canterbury since the English Reformation to be appointed to this office from outside the Church of England.
His election by the Chapter of Canterbury Cathedral was confirmed by nine bishops in the customary ceremony in London on 2 December 2002, when he officially became Archbishop of Canterbury.
He was enthroned at Canterbury Cathedral on 27 February 2003 as the 104th Archbishop of Canterbury.

The translation of Williams to Canterbury was widely canvassed.
As a bishop he had demonstrated a wide range of interests in social and political matters and was widely regarded, by academics and others, as a figure who could make Christianity credible to the intelligent unbeliever.
As a patron of Affirming Catholicism, his appointment was a considerable departure from that of his predecessor and his views, such as those expressed in a widely published lecture on homosexuality were seized on by a number of evangelical and conservative Anglicans.
The debate had begun to divide the Anglican Communion, however, and Williams, in his new role as its leader was to have an important role.

As Archbishop of Canterbury, Williams acted ex officio as visitor of King's College London, the University of Kent and Keble College, Oxford, governor of Charterhouse School, and, since 2005, as (inaugural) chancellor of Canterbury Christ Church University.
In addition to these ex officio roles, Cambridge University awarded him an honorary doctorate in divinity in 2006; in April 2007, Trinity College and Wycliffe College, both associated with the University of Toronto, awarded him a joint Doctor of Divinity degree during his first visit to Canada since being enthroned and he also received honorary degrees and fellowships from various universities including Kent, Oxford, and Roehampton.

Williams speaks or reads eleven languages: English, Welsh, Spanish, French, German, Russian, Biblical Hebrew, Syriac, Latin, and both Ancient (koine) and Modern Greek.
He learnt Russian in order to be able to read the works of Dostoyevsky in the original.
 He has since described his spoken German as a "disaster area" and said that he is "a very clumsy reader and writer of Russian".

Williams is also a poet and translator of poetry.
His collection The Poems of Rowan Williams, published by Perpetua Press, was longlisted for the Wales Book of the Year award in 2004.
Beside his own poems, which have a strong spiritual and landscape flavour, the collection contains several fluent translations from Welsh poets.
He was criticised in the press for allegedly supporting a "pagan organisation", the Welsh Gorsedd of Bards, which promotes Welsh language and literature and uses druidic ceremonial but is actually not religious in nature.
His wife, Jane Williams, is a writer and lecturer in theology.
They married on 4 July 1981 and have two children who were also state educated.

In 2005, Prince Charles married Camilla Parker Bowles, a divorcee, in a civil ceremony.
Afterwards, Williams, gave the couple a formal service of blessing.
In fact, the arrangements for the wedding and service were strongly supported by the Archbishop "consistent with the Church of England guidelines concerning remarriage" The "strongly-worded" act of penitence by the couple, a confessional prayer written by
On 5 December 1991, Williams was elected Bishop of Monmouth in the Church in Wales: he was consecrated a bishop on 1 May 1992 at St Asaph Cathedral and enthroned at Newport Cathedral on 14 May. He continued to serve as Bishop of Monmouth after he was elected to also be the Archbishop of Wales in December 1999, in which capacity he was enthroned again at Newport Cathedral on 26 February 2000.
In 2002, he was announced as the successor to George Carey as Archbishop of Canterbury — the senior bishop in the Church of England. The Archbishop of Canterbury in England acts as a focus of unity recognised as primus inter pares ("first among equals") but does not exercise authority in Anglican provinces outside the Church of England. As a bishop of the disestablished Church in Wales, Williams was the first Archbishop of Canterbury since the English Reformation to be appointed to this office from outside the Church of England. His election by the Chapter of Canterbury Cathedral was confirmed by nine bishops in the customary ceremony in London on 2 December 2002, when he officially became Archbishop of Canterbury. He was enthroned at Canterbury Cathedral on 27 February 2003 as the 104th Archbishop of Canterbury.
The translation of Williams to Canterbury was widely canvassed. As a bishop he had demonstrated a wide range of interests in social and political matters and was widely regarded, by academics and others, as a figure who could make Christianity credible to the intelligent unbeliever. As a patron of Affirming Catholicism, his appointment was a considerable departure from that of his predecessor and his views, such as those expressed in a widely published lecture on homosexuality were seized on by a number of evangelical and conservative Anglicans. The debate had begun to divide the Anglican Communion, however, and Williams, in his new role as its leader was to have an important role.
As Archbishop of Canterbury, Williams acted ex officio as visitor of King's College London, the University of Kent and Keble College, Oxford, governor of Charterhouse School, and, since 2005, as (inaugural) chancellor of Canterbury Christ Church University. In addition to these ex officio roles, Cambridge University awarded him an honorary doctorate in divinity in 2006; in April 2007, Trinity College and Wycliffe College, both associated with the University of Toronto, awarded him a joint Doctor of Divinity degree during his first visit to Canada since being enthroned and he also received honorary degrees and fellowships from various universities including Kent, Oxford, and Roehampton.
Williams speaks or reads eleven languages: English, Welsh, Spanish, French, German, Russian, Biblical Hebrew, Syriac, Latin, and both Ancient (koine) and Modern Greek. He learnt Russian in order to be able to read the works of Dostoyevsky in the original.  He has since described his spoken German as a "disaster area" and said that he is "a very clumsy reader and writer of Russian".
Williams is also a poet and translator of poetry. His collection The Poems of Rowan Williams, published by Perpetua Press, was longlisted for the Wales Book of the Year award in 2004. Beside his own poems, which have a strong spiritual and landscape flavour, the collection contains several fluent translations from Welsh poets. He was criticised in the press for allegedly supporting a "pagan organisation", the Welsh Gorsedd of Bards, which promotes Welsh language and literature and uses druidic ceremonial but is actually not religious in nature. His wife, Jane Williams, is a writer and lecturer in theology. They married on 4 July 1981 and have two children who were also state educated.
In 2005, Prince Charles married Camilla Parker Bowles, a divorcee, in a civil ceremony. Afterwards, Williams, gave the couple a formal service of blessing. In fact, the arrangements for the wedding and service were strongly supported by the Archbishop "consistent with the Church of England guidelines concerning remarriage" The "strongly-worded" act of penitence by the couple, a confessional prayer written by
Rowan Williams