He amassed La Liga totals of 241 games and 32 goals over the course of ten seasons, representing in the competition Deportivo, Málaga, Atlético Madrid and Villarreal and winning four major titles with the third club, including the 2013–14 league championship.
Born in Teverga, Asturias, Adrián was a product of local Real Oviedo's youth system. He quickly made the transition into the first team, scoring three goals in 26 matches while playing in Segunda División B. However, he did not have a professional contract because he was a youth player, and the only way to acquire his services for free was to offer him a professional contract.
Deportivo de La Coruña obliged and, in October 2006, Oviedo were given a €331,000 compensation by the La Liga club. Adrián's finest moment of the 2006–07 season arrived when, on 31 March 2007, he entered Deportivo's league match at the Camp Nou in the 61st minute, and although FC Barcelona won it 2–1, he managed to score with a clever touch; it was his only league goal of the campaign, in 15 appearances (six starts).
After receiving few first team opportunities during 2007–08, Adrián was loaned to Segunda División strugglers Deportivo Alavés in April 2008. After helping the Basque team avoid relegation with three league goals, he returned to A Coruña to be loaned again on 14 August, this time to newly promoted Málaga CF on a season-long deal.
On 28 September 2008, Adrián netted his first goal for Málaga in a 2–1 home win over Real Valladolid, and appeared regularly throughout the campaign albeit only scoring three times. For 2009–10 he returned to Deportivo, where he began to feature prominently in the starting XI in various offensive positions. On 23 March 2010, he equalized for 10-men – eventually nine – Depor at Sporting de Gijón, in a final 1–2 loss.
Adrián continued to appear regularly for Deportivo in the 2010–11 season, again as a starter. In the campaign's Copa del Rey, the Galicians faced Córdoba CF in the round-of-16: after a 1–1 draw in Andalusia, he scored the 1–1 in the 90th minute of the second leg, taking the match to extra time where he netted two more for a 3–1 win and a spot in the quarter-finals. He finished as the team's top scorer at seven in 36 games, but they returned to the second level after 20 years.
Adrián joined Atlético Madrid on 19 July 2011 as a free agent, signing a four-year deal. Nine days later, in his official debut, he assisted in both José Antonio Reyes goals in a 2–1 home win against Strømsgodset IF, for the season's UEFA Europa League; in the second leg, he netted the opening goal in a 2–0 success.
In the same competition, on 25 August 2011, Adrián added a brace in a 4–0 away win against Vitória de Guimarães, which ensured Atlético's qualification to the group stage 6–0 on aggregate. His first league goal came in a 4–0 home success over Racing de Santander on 18 September, heading in the closer from an Arda Turan cross.
As volatile Reyes became increasingly disgruntled with his reserve status at the club, Adrián firmly established himself in the starting eleven. In two games separated by only five days, he scored four goals, two apiece against Real Zaragoza in the league (3–1 home win) and Udinese Calcio (4–0, also at home) in the Europa League; in the latter competition, as the team reached and won the final, he scored 11 goals all rounds comprised.
On 17 December 2013, Adrián extended his link with the Colchoneros until 30 June 2018. On 30 April of the following year, he scored his third official goal of the season, starting and netting the opener to help his team win 3–1 at Chelsea and progress to the final of the UEFA Champions League for the first time since 1974.
On 12 July 2014, Adrián signed a five-year deal with Portuguese club FC Porto, who paid €11 million to Atlético Madrid for 60% of his economic rights. He scored his first goal for his new team on 17 September, in a 6–0 win over FC BATE Borisov for the Champions League group stage; it was his only goal in 17 official appearances over his first season.
On 31 August 2015, Adrián returned to Spain and its top division after agreeing to a one-year loan deal with Villarreal CF. After several months on the sidelines with a left leg tendon ailment, he scored his first goal the following 28 February, concluding a 3–0 home win over Levante UD.
On 28 April 2016, Adrián scored the only goal at the Estadio El Madrigal against Liverpool, coming on for Roberto Soldado late into the second half and netting in the 90th minute of the first leg of the Europa League semi-finals. The following January, after few opportunities at Porto, he returned to Villarreal on the same basis for the remainder of the campaign.
On 11 August 2017, Adrián returned to Deportivo on a one-year loan deal.
In the 2007 FIFA U-20 World Cup held in Canada, Adrián scored a hat-trick for Spain in the final group stage game against Jordan on 7 July, with all three goals coming in a span of ten minutes late in the first half.
Subsequently, he represented the under-21s in two UEFA European Championships. In the 2011 edition in Denmark, Adrián scored a brace in a 2–0 group stage win against the Czech Republic, adding another in the next match against Ukraine (3–0). In the semi-final against Belarus, he scored the late 1–1 equalizer which took the game into extra time, adding another in that period in an eventual 3–1 triumph; he was awarded the Golden Boot as the highest scorer in the tournament.
Adrián made his full side debut on 26 May 2012 in a friendly with Serbia: after replacing Soldado at half-time, he scored with a header in the 64th minute, and later gained a penalty kick which resulted in the final 2–0 in St. Gallen. He was also part of the Olympic team in 2012.As of 24 May 2014
UEFA Europa League: 2011–12
La Liga: 2013–14
UEFA Super Cup: 2012
Copa del Rey: 2012–13
UEFA Champions League: Runner-up 2013–14
Supercopa de España: Runner-up 2013
UEFA European Under-21 Championship: 2011
FIFA U-20 World Cup: Silver Shoe 2007
UEFA European Under-21 Championship: Golden Boot, Team of the Tournament 2011