Having received the booking during the 4-0 victory over Rayo Vallecano on Tuesday, the Spain international will automatically miss Barca's next fixture, against Levante this Saturday, and return for the showdown against Los Blancos in the following game with his yellow card limit wiped clean.
However, Pique could now face a two-game ban if it is deemed that the booking he earned against Rayo was deliberate.
Modifications had been made to the Royal Spanish Football Federation (RFEF) Disciplinary Code in 2011, which states that any deliberate intent to receive a fifth yellow card can lead to an additional match suspension.
Article 112 of the Disciplinary Code reads: "Any player, who during the course of a game, provokes a fifth booking may be sanctioned with, in addition to the penalty provided for in the first paragraph of this article [a standard one-game ban], an extra one game suspension and fined the amount of €600. In determining the intent of the player, circumstances will be taken into account such as the nature of the breaching of the game rules and the attitude of the player during the match."
Evidence that will be taken into account include minutes taken by referee Perez Lasa during the Barcelona match against Rayo.
According to AS, Lasa noted in his referee match report: "On 83 minutes the player (3) Gerard Pique was booked for the following reason: Delaying the restart of play for his team with the intention of wasting time."
Barcelona are currently three points behind Real Madrid in the Primera Division league table, but have played one game more.
Starting last week and continuing every Friday through to January, Goal.com will publish extracts from Graham Hunter's highly-anticipated book, Barca: The Making of the Greatest Team in the World. Friday's second extract was about how Joan Laporta and Sandro Rosell used David Beckham as a vote-winner in the club elections of 2003, even though a deal was already done between Manchester United and Real Madrid.