The 25-year old centre-back has demanded an explanation as to why his Blaugrana team-mate failed to collect the prize alongside Iker Casillas and Xavi
The accolade was handed to Spain duo Xavi and Iker Casillas in recognition of their achievements in football, after the pair were key figures of the squad that won back-to-back European Championships and the 2010 World Cup.
"I sincerely cannot understand why Puyol is not collecting the Prince of Asturias prize with Iker and Xavi," he wrote on Twitter.
"Just like Xavi and Iker, Puyol represents all these years of success that the national side has had. They were the first players who started this generation."
Although Pique felt the non-inclusion of Puyol was unjust, he was quick to praise both the winners.
"Many congratulations to Iker and Xavi! You deserve it! I'm very proud to be your team-mate."