Spain’s national team trained for just 23 minutes in their open training session at their base in Las Rozas just outside of Madrid.
As the side returned to the dressing rooms, Gerard Pique was guarded by security guards as spectators threw objects in the direction of the Barcelona defender.
The news comes after Sunday’s controversial referendum on independence in Catalonia, in which Pique voted and was a public supporter of the right of the Catalan people to vote.
After featuring for Barcelona in their behind closed doors win over Las Palmas, the former Manchester United man was emotional as he insisted that if his presence was a problem for manager Julian Lopetegui or anyone in the squad then he would bring his retirement from international duty forward from after the Russia World Cup in 2018.
Lopetegui has previously supported Pique in public after years of fans whistling and booing him in the shirt of Spain.
On Friday, Spain face Albania in a crucial World Cup Qualifier at the Jose Rico Perez stadium in Alicante, home to third tier team Hercules. It is unclear if Pique will start or even be involved for his country.
Spain will already be without key players like Barcelona midfielder Andres Iniesta and Chelsea forward Alvaro Morata after both picked up injuries over the weekend.