Both sides have won their first two matches of the 2013-14 campaign, with new Real manager Carlo Ancelotti overseeing triumphs against Real Betis and Granada.
Frenchman Karim Benzema has netted in both of those victories, while Portuguese star Cristiano Ronaldo has not scored this season amid reports linking him with a return to Manchester United.
Ronaldo's failure to score on the last day of the 2012-13 season means that he has played three successive league fixtures for Real without finding the net.
While the reports linking Gareth Bale to Real Madrid continue, Ancelotti is still short of genuine firepower up front following Gonzalo Higuain's departure to Napoli.
Whether midfielder Ander Herrera features is sure to be a talking point, with Athletic revealing on Friday that they had rejected a €30million bid for their star man.
Athletic president Josu Urrutia said on Friday: "There is an offer for Ander Herrera. For a player to go first the player has to express his desire to leave the club.
"Herrera has not told us he wants to go, and we have said we do not negotiate for our players."
Of the last 16 La Liga encounters between the two sides, Real have won 15 of them, with Athletic's sole triumph coming in January 2010 when Fernando Llorente headed the winner.
