Neipperg married Therese Josephine Walpurgis, Countess Thurn-Valsassina (1778-1815) in 1806 and they had four sons.
He was succeeded in the headship of the House of Neipperg by his eldest son Alfred (1807–1865) who married, secondly, Princess Marie Frederike Charlotte (1816-1887), daughter of King William I of Württemberg.
Alfred died childless and his brother Erwin Franz (1813–1897) followed him.
The male heirs of this senior line of counts still live at Schwaigern in Germany.
The present head of the house, Karl-Eugen, Count von Neipperg (born 1951), is the husband of Archduchess Andrea von Habsburg.

In August 1814, he was instructed to escort Napoleon's wife, the Empress Marie-Louise, to Aix-les-Bains to take the waters.
However, the true purpose of his mission was to prevent the Empress from joining Napoleon in exile in Elba.
Neipperg, who had understood this perfectly, was rumored to have told his mistress in Milan: "Inside of six months I shall be her lover, and soon her husband."
The quote is most likely apocryphal, and at any rate, he did not need that long, as Marie-Louise soon fell into his arms and talk of Elba never arose again.

Four months after the death of Napoleon in 1821, he married Marie-Louise in a morganatic marriage.
She had become sovereign Duchess of Parma, Piacenza and Guastalla, styled Maria-Luigia di Parma, in the final act of the Congress of Vienna on 9 June 1815.
From this union, four children were born, the first two before the marriage, whilst Maria-Luigia was still legally married to Napoleon:
Countess Albertine di Montenuovo (Italian translation of Neipperg) (1817–1867), who married Luigi Sanvitale, Count di Fontanellato;
William Albert, Count then 1st Prince von Montenuovo, (1819–1895), who married Countess Juliana Batthyány von Németújvár;
Countess Mathilde di Montenuovo, born in 1822, died young.

Count Gustavo di Montenuovo, born in 1823, died young.

Neipperg died in Parma on 22 February 1829 of a heart condition.
His descendants with the Duchess Maria-Luigia, the Princes von Montenuovo, intermarried with the Austro-Hungarian nobility and served as courtiers and diplomats at the Imperial Hofburg in Vienna, dying out in the male line in 1951.
Neipperg married Therese Josephine Walpurgis, Countess Thurn-Valsassina (1778-1815) in 1806 and they had four sons. He was succeeded in the headship of the House of Neipperg by his eldest son Alfred (1807–1865) who married, secondly, Princess Marie Frederike Charlotte (1816-1887), daughter of King William I of Württemberg. Alfred died childless and his brother Erwin Franz (1813–1897) followed him. The male heirs of this senior line of counts still live at Schwaigern in Germany. The present head of the house, Karl-Eugen, Count von Neipperg (born 1951), is the husband of Archduchess Andrea von Habsburg.
In August 1814, he was instructed to escort Napoleon's wife, the Empress Marie-Louise, to Aix-les-Bains to take the waters. However, the true purpose of his mission was to prevent the Empress from joining Napoleon in exile in Elba. Neipperg, who had understood this perfectly, was rumored to have told his mistress in Milan: "Inside of six months I shall be her lover, and soon her husband." The quote is most likely apocryphal, and at any rate, he did not need that long, as Marie-Louise soon fell into his arms and talk of Elba never arose again. 
Four months after the death of Napoleon in 1821, he married Marie-Louise in a morganatic marriage. She had become sovereign Duchess of Parma, Piacenza and Guastalla, styled Maria-Luigia di Parma, in the final act of the Congress of Vienna on 9 June 1815. From this union, four children were born, the first two before the marriage, whilst Maria-Luigia was still legally married to Napoleon:
Countess Albertine di Montenuovo (Italian translation of Neipperg) (1817–1867), who married Luigi Sanvitale, Count di Fontanellato;
William Albert, Count then 1st Prince von Montenuovo, (1819–1895), who married Countess Juliana Batthyány von Németújvár;
Countess Mathilde di Montenuovo, born in 1822, died young.
Count Gustavo di Montenuovo, born in 1823, died young.
Neipperg died in Parma on 22 February 1829 of a heart condition. His descendants with the Duchess Maria-Luigia, the Princes von Montenuovo, intermarried with the Austro-Hungarian nobility and served as courtiers and diplomats at the Imperial Hofburg in Vienna, dying out in the male line in 1951.
Adam Albert von Neipperg