In his first season Barberá established himself as the most promising rider of the three and in 2003 he broke through, with his first victory at Donington Park making him one of the youngest riders ever to win a Grand Prix. A strong finish to the season saw him take third place in the championship and he signed up for a title challenge with Seedorf Racing in 2003.[2] Several inopportune crashes and mechanical failures derailed his hopes but victory in the final race secured the runner-up spot and a factory ride with Fortuna Honda in the 250cc class for 2005.[2] After two years with the team he moved to Team Toth in 2007.[2]
Barberá survived a huge crash during the Italian round of the championship on June 1, 2008. Running second behind Marco Simoncelli on the penultimate lap who tried to defend his lead by changing his line on the straight, Barberá slipstreamed onto Simoncelli's back wheel and clipped it with his front brake lever. His bike somersaulted through the air, with Barberá escaping somewhat uninjured. However, a further crash in practice at Motegi left him with two spinal fractures, ending his season.[3]
In the 2009 250cc world championship, Barberá won three races along with five other podium results to finish second to Honda's Hiroshi Aoyama.[2] Barberá won the 2009 Valencia Grand Prix, the final two-stroke, 250cc race in Grand Prix history, as the class was to be discontinued in favor of the four-stroke Moto2 class in 2010.[2] On 20 August 2009 it was announced Barberá would move to MotoGP in 2010, riding for the Aspar Team aboard Ducati customer bikes.[4][5] Barberá finished the 2010 MotoGP season in twelfth place, and followed on in eleventh place in 2011. On 7 November 2011, it was announced that he was moving to Pramac Racing for the 2012 season.[6]
In 2016, Barbera finished a career best of tenth place in the MotoGP standings. That year, he had his only two races for a factory MotoGP team, replacing Andrea Iannone at Ducati Corse.[7] Barbera switched to Moto2 after failing to find a MotoGP ride for 2018.[8] He competed at the last Grand Prix of his career that year at Mugello.[9]
Barbera was sentenced to six months in jail for assault and battery in 2013.[12]
He was ordered to serve 22 days of community service in 2018 for driving under the influence, which caused him to lose his Pons Racing Moto2 ride.[9][13]
Barbera was accused of stealing a Yamaha Supersport bike owned by his own team, Team Toth, in 2019.[14][15]
In 2023, he was investigated for fraud and forgery.[16][17] It was also revealed by Andorran news website Altaveu that he had a search and arrest warrant issued against him since 2019 for another undisclosed affair.[18]