Pique was unsurprisingly selected from the start in Kazan as La Roja earned their first win of the tournament with a 1-0 victory over Iran, after being held to a thrilling 3-3 draw by Portugal in their Group B opener last Friday.
The Barcelona defender made his debut for the national team in 2009 and helped them to glory at the 2010 World Cup and 2012 European Championship.
His national team career has not been without controversy however, with Pique having often been jeered by Spain fans for his views on Catalan independence.
But he now becomes the 13th centurion for Spain, moving level on 100 caps with fellow Barca great Carles Puyol. Iker Casillas is Spain's record caps holder with 167.
It becomes the latest story in an eventful few weeks for Pique, as he has made news for things both on the field and off since the start of the 2018 World Cup.
Pique became a key figure at the end of Spain's opener against Portugal, as his foul on Ronaldo allowed the Real Madrid star the opportunity to equalise the contest with a free-kick that completed his hat-trick.
After the contest, Pique claimed Ronaldo has a habit of throwing himself to the ground.
Off the field, Pique has also been involved in drama surrounding Antoine Griezmann's decision to shun Barcelona and remain at Atletico Madrid.
Griezmann televised his decision through a documentary produced by Pique's investment company Kosmos.
Since, Pique has been forced to defend himself against accusations he has betrayed his club, while Barca have said they will hold internal discussions with the defender and Samuel Umtiti over the matter.