Luis Enrique's men could not break down Getafe in a 0-0 stalemate last time out in the top flight but can put the pressure back on Carlo Ancelotti's leaders - given the latter's league duties are complete for 2014, due to Club World Cup commitments.
Barca were also buoyed by an 8-1 Copa del Rey victory over Huesca on Tuesday, with Pedro on target with a hat-trick in the 12-1 aggregate triumph.
The meeting will be the sides' first in La Liga, with Barca winning their Copa del Rey tie in 2012-13 7-0 on aggregate - including a 5-0 win at Camp Nou.
Diego Simeone's men lost at home to in-form Villarreal, and are again on the road at the San Mames to face Athletic Bilbao.
Valencia and Villarreal have the chance to finish the year in fourth, given Sevilla's clash with Real was postponed.
Nuno Espirito Santo's men are on the road at Eibar, who held Sevilla last time out, while Villarreal can make it five straight wins to enter 2015 in a flurry if they surpass lowly Deportivo La Coruna at home.
