On 27 April 2009, La Liga club Villarreal signed the 20-year-old Montero to a five-year contract effective from July.
He contributed two goals and five assists as the Valencians trounced amateurs Navata 27–0 in a pre-season friendly.
He made his competitive debut for the senior side in the Europa League round of 32 in February 2010, replacing Robert Pires with 20 minutes left as Villarreal were eliminated by Wolfsburg, but spent the vast majority of his first season with the reserves as one of their most important attacking elements as they overachieved to finish seventh in their first season in the Segunda División.

Subsequently, Montero was promoted to the main squad as a complement for the more experienced Santi Cazorla and Cani.
He made his top-flight debut in the opening fixture of the 2010–11 La Liga season, replacing Cani in a 0–1 loss at Real Sociedad.

Montero failed to find a regular first-team place at Villarreal, and moved to another La Liga club, Levante, in late January 2011 on loan for the rest of the season.
He spent the following season on loan at another top-flight club, the newly promoted Real Betis.
He scored his first goal of the campaign on 10 March 2012 in a 2–3 home defeat against Real Madrid.
He was first choice throughout most of his tenure with the Pepe Mel-led squad, who managed to retain their league status.
On 27 April 2009, La Liga club Villarreal signed the 20-year-old Montero to a five-year contract effective from July. He contributed two goals and five assists as the Valencians trounced amateurs Navata 27–0 in a pre-season friendly. He made his competitive debut for the senior side in the Europa League round of 32 in February 2010, replacing Robert Pires with 20 minutes left as Villarreal were eliminated by Wolfsburg, but spent the vast majority of his first season with the reserves as one of their most important attacking elements as they overachieved to finish seventh in their first season in the Segunda División.
Subsequently, Montero was promoted to the main squad as a complement for the more experienced Santi Cazorla and Cani. He made his top-flight debut in the opening fixture of the 2010–11 La Liga season, replacing Cani in a 0–1 loss at Real Sociedad.
Montero failed to find a regular first-team place at Villarreal, and moved to another La Liga club, Levante, in late January 2011 on loan for the rest of the season. He spent the following season on loan at another top-flight club, the newly promoted Real Betis. He scored his first goal of the campaign on 10 March 2012 in a 2–3 home defeat against Real Madrid. He was first choice throughout most of his tenure with the Pepe Mel-led squad, who managed to retain their league status.
Jefferson Montero