In the 2006 season, Ayón saw some action off the bench for Halcones UV Xalapa, as the team finished second in the Liga Nacional de Baloncesto Profesional.[4] Ayón cracked the team's starting lineup the following season, and eventually led Halcones to back-to-back Mexican league titles, in 2007–08 and 2008–09.[3] He averaged 10.2 points and 8.1 rebounds per game in 2007–08, and improved on that by averaging 13.2 points and 7.8 rebounds per game the following season.[3] In what turned out to be his final game for the team, Ayón turned in a dominant, 24-point, 20-rebound, performance in leading his club to a 94–90 overtime victory over Soles de Mexicali, that clinched their second consecutive league title.[5]
In December 2011, Ayón signed with the New Orleans Hornets, of the NBA, after paying Baloncesto Fuenlabrada with a $1.5-million buy-out clause. Ayón received a three-year contract, with the last year being a team option.[7]
On July 29, 2013, Ayón was claimed off waivers by the Atlanta Hawks.[11] On February 12, 2014, Ayón scored a career high 18 points, in a 83–104 loss to the Toronto Raptors.[12] On February 28, 2014, it was announced that Ayón would miss the rest of the 2013–14 season, following successful surgery to repair a right shoulder injury.[13]
Ayón was named the EuroLeague MVP of the Round, in the first week of the playoffs, in the 2014–15 season,[17] and in week nine of the regular season of the 2015–16 season.[17]
On July 14, 2016, Ayón signed a new three-year contract with Real Madrid.[17]
In May 2018, Real Madrid won the 2017–18 EuroLeague championship, after defeating Fenerbahçe Doğuş in the final game with 85–80.[19] Over 17 EuroLeague games, Ayón averaged 9.6 points, 6.1 rebounds and 2.9 assists per game.
In June 2018, Ayón helped guide Real Madrid to the 2017-18 ACB Spanish League Championship by defeating Kirolbet Baskonia.[20]
In June 2019, Ayón helped lead Real Madrid to the 2018-19 ACB Spanish League Championship by defeating FC Barcelona Lassa[21]
Russia
On July 26, 2019, Ayón signed a one-year deal with Zenit Saint Petersburg of the VTB United League and the EuroLeague.[22] He averaged 12 points, 5 rebounds and 2 assists per game. Ayón parted ways with the team on July 26, 2020.[23]
On August 20, 2022, Ayón announced his initial retirement from professional basketball.,[27] however, in April 2023 he announced that he would come out of retirement to play for Venados de Mazatlán[28]
In August 2014, Ayón led Mexico to victory in the gold medal game against Puerto Rico at the 2014 Centrobasket. Ayón was named the MVP of the tournament.[30] Later that month, he joined Mexico for the 2014 FIBA World Cup.
In 2015, Ayón was named to the 2015 FIBA Americas Championship All-Tournament Team, after tallying 17.7 points per game (2nd in the tournament), 12.4 rebounds per game (1st in the tournament), 3.5 assists per game (7th in the tournament), 1.3 steals per game (3rd in the tournament), and 1.2 blocks per game (1st in the tournament).