The Barcelona star and his Real Madrid counterpart have been rewarded for their role in Spain's success in the past few years
The Barcelona midfielder and Real Madrid goalkeeper, who were put forward by Fifa president Sepp Blatter, got 11 out of the 18 votes, and will receive the award at a ceremony at Oviedo's Campoamor theatre on October 26.
"They asked me in my capacity as judge for the awards, to offer an idea, and the first names that came to me were Casillas and Xavi. Not only for what they've won on the pitch, but what they've demonstrated off it," Blatter stated to AS.
"Because they represent the unity of Spain over and above the differences there are between Madrid and Barca. They're friends first and opponents later, and they put this friendship above the rivalry.
"It's something uncommon in football and as president, I'm proud. That's why I proposed them for the Prince of Asturias award."
The award was won by athlete Haile Gebreselassie last year, while Spain's national team came out victorious in 2010.