Sevilla held on for a 3-2 win over Villarreal in an entertaining match at the Sanchez Pizjuan, while Argentina forward Sergio Aguero struck twice in Atletico's 4-1 win over mid-table Levante at the Calderon.
"These were some vital points against a very powerful rival," Sevilla coach Gregorio Manzano said in an interview with Spanish television.
Both teams have 49 points with five games left. Sevilla are sixth ahead of Atletico thanks to a superior head-to-head record and two behind fifth-placed Athletic Bilbao who won 2-1 at local Basque rivals Real Sociedad on Saturday.
Espanyol's miserable recent run continued when they lost 1-0 at Sporting Gijon and stay eighth on 45 points, while Villarreal, who are through to the semi-finals of this season's Europa League, remain fourth on 57.
Ivan Rakitic stroked a free-kick into the top corner and Alvaro Negredo caught Villarreal goalkeeper Diego Lopez off his line to put Sevilla 2-0 ahead inside a quarter of an hour in the Andalusian capital.
Carlos Marchena, who was shown a second yellow card and sent off in the 85th minute, pulled a goal back 11 minutes after half-time before substitute Ndri Romaric restored the home side's two-goal cushion in the 62nd.
Giuseppe Rossi came off the bench to curl in a superb second for the visitors with around 20 minutes left and later hit the post but Sevilla held on during a frantic finale.
At the Calderon in the earlier kick-off, Brazilian midfielder Elias fired Atletico ahead in the 19th minute when he arrowed a free-kick over the Levante wall and into the net off the underside of the crossbar.
Ecuadorian striker Felipe Caicedo levelled from the penalty spot six minutes before the break and Aguero made it 2-1 five minutes into the second half when he pounced on a loose ball and smashed a low shot in off the post from just outside the area.
His second came from another penalty with 20 minutes remaining and Levante goalkeeper Gustavo Munua gifted the home side a fourth in the 84th minute when he fluffed an attempted clearance at a corner and diverted the ball into his own net.
At the other end of the table, Malaga took another step towards safety with a 2-1 win at Racing Santander, while Hercules secured a potentially vital 1-0 win at Deportivo La Coruna. Getafe's woes deepened when they lost 2-0 to Michael Laudrup's Real Mallorca.
Barcelona maintained their eight-point lead over Real Madrid at the top when they beat Osasuna 2-0 at the Nou Camp on Saturday. Real, who secured their first King's Cup since 1993 at Barca's expense on Wednesday, routed Valencia 6-3.
