Injured Puyol pulls out of Spain squad
The Barcelona defender failed to complete the side's first training session in Las Rozas near Madrid and tests showed he had damaged a calf muscle.
Osasuna defender Nacho Monreal has been called up as a replacement.
The world champions start the defence of their European title with a Euro 2012 qualifier against Liechtenstein in Vaduz on Friday. They travel to play Argentina in a friendly four days later.