Real Madrid travel to Sevilla in round 35 of La Liga on Saturday, the same day league leaders Barcelona visit relegation-bound Cordoba.
Real Madrid are within touching distance of table-topping Barcelona but veteran goalkeeper Iker Casillas said he would take the UEFA Champions League title over La Liga.
Only two points separate Real and Barca with four matches remaining in La Liga, after both teams claimed respective wins during the week.
Real accounted for relegation-threatened Almeria 3-0 on Wednesday, while Barca consolidated top spot via a 6-0 drubbing of Getafe a day earlier.
Carlo Ancelotti's Real are back in action on Saturday as they prepare to visit fifth-placed Sevilla, who are still in the hunt for Champions League qualification.
However, winning an unprecedented second consecutive Champions League title is the aim for Real, who face Juventus in the semi-finals of the competition.
"The coach already pointed out that the Champions League is easier to win," Casillas said on Thursday.
"The Champions League is still in our hands whilst the league title is currently in Barca's hands. The last four teams remaining in the Champions League all have a 25 per cent chance of winning.
"Traditionally Madrid fans prefer European competition and winning the highest honour in Europe for the second year running would be special as it's never been done before."
Sevilla are level on 69 points with Valencia, who occupy the fourth and final Champions League spot on goal difference following their 1-1 draw at Rayo Vallecano on Thursday.
Valencia host out-of-form Eibar on Sunday.
Barca are on the road against Cordoba on Saturday, with victory enough to consolidate their two-point buffer at the summit.
Lionel Messi and Luis Suarez both scored twice during the week as Barca's unbeaten streak in all competitions extended to 15 games.
"The season so far is excellent. Based on the results, we're back on the path to excellence," Barca president Josep Maria was quoted as saying by Marca.
"The team is highly motivated; we've managed to put together the best front line in the world, and all under a new coach."
Cordoba have all but been relegated to the second tier of Spanish football, with the club 11 points adrift at the foot of the table with 12 points still up for grabs.
Elsewhere on Saturday, third-placed Atletico Madrid entertain Athletic Bilbao.
Deportivo La Coruna - 18th in the standings - tackle Villarreal.
On Sunday, Malaga go head-to-head with Elche, Granada make the trip to Getafe and Espanyol play Rayo.
Almeria versus Celta Vigo is the Monday fixture, while Real Sociedad and Levante kick-off the round on Friday.