Sergio Ramos set a new record for red cards in LaLiga after receiving his marching orders for the 19th time in the 0-0 draw with Athletic Bilbao on Saturday.
The 31-year-old was shown a second yellow for leading with the elbow on Aritz Aduriz in the 86th minute at San Mames.
Ramos' dismissal - his second of the campaign - took him clear of former Barcelona and Sevilla defender Pablo Alfaro and Real Zaragoza legend Xavi Aguado.
The defender wore a face mask throughout Saturday's match in what was his return from a broken nose suffered against rivals Atletico Madrid two weeks ago.
But the late sending off compounded a frustrating result for Zinedine Zidane's side as they missed a chance to close to within six points of leaders Barcelona.