Atletico Madrid have a chance to pile more King's Cup misery on neighbours Real after eliminating Athletic Bilbao on Wednesday to set up a last-four clash against the bitter city rivals they beat in last year's final.
James Rodriguez headed the opener before going off injured in Real Madrid's win.
Following a bright start to the season it was another disappointing display by Villarreal, who have one win from seven games in La Liga, before the return at El Madrigal in two weeks.
Neymar took time to settle but is finally shining in Barcelona's devastating attacking trident with Villarreal the next La Liga opponents in their sights on Sunday as the Catalans continue their pursuit of Real Madrid.
News of all that's transpired on and off the football field
A round-up of Saturday's action in La Liga, Ligue 1 and Serie A.
Barcelona have been boosted by the successful return from injury of talismanic playmaker Andres Iniesta as they prepare to host city rivals Espanyol in La Liga on Sunday.
Red Star, who won the European Cup in 1991 and reached the latter stages the following season, finished second in Group H behind Arsenal who crushed BATE Borisov 6-0.
Athletic Bilbao missed a chance to tighten their grip on Spain's fourth Champions League qualification place when they had to come from behind to rescue a 1-1 draw at 10-man Villarreal in La Liga on Monday.
Holders Barcelona crashed out of the Champions League after being stifled by a brilliantly well-organised Atletico Madrid.
News of all that's transpired on and off the football field
News of all that's transpired on and off the football field
Centre-back Eric Abidal and midfielder Samir Nasri were missing when France coach Didier Deschamps named a 24-man squad on Thursday for next week's friendly against the Netherlands.
Joao Miranda and new signing Mario Mandzukic led Atletico Madrid to a 2-1 home win in La Liga on Saturday as visitors Eibar were unable to cope with the aerial threat of the champions.
Underlying tensions mean Luis Enrique will not be remembered with the same reverence as Pep Guardiola, even though he has delivered a similar trophy haul.
Cristian Tello hit a hat-trick as Barcelona came from behind to win 4-1 in their King's Cup quarter-final first leg at Levante on Wednesday and Lionel Messi celebrated his 400th appearance for the Catalan side.
News of all that's transpired on and off the football field
A late goal by Toni Kroos sealed victory as Real Madrid defeated an impressive Celta Vigo side 2-1 to win their first home La Liga game of the campaign on Saturday.
Antoine Griezmann headed two goals for Atletico Madrid in a 3-1 victory over Levante that kept them on the heels of La Liga leaders Real Madrid on Saturday.
IMAGES from La Liga matches played on Sunday
Messi stretched Barca's lead by finishing off a brilliant move with Luis Suarez in the 50th minute and the Uruguayan joined his close friend and strike partner on 15 league goals by robbing an Eibar defender and finishing inside the near post in the 68th.
IMAGES from the 2020 Euro Qualifiers played on Monday
Photographic summary of the football matches played across Spain, Italy and France
Real Madrid captain Sergio Ramos again came to his side's rescue as they snatched a dramatic 3-2 victory over Deportivo La Coruna on Saturday to keep Zinedine Zidane's side six points clear at the top of La Liga and set a club record 35 games unbeaten.
The victory saw the unfashionable Madrid club tighten their grip on the coveted fourth spot in the table by moving on to 58 points after 36 games, three points clear of nearest challengers Sevilla, who lost to Leganes on Friday.
Champions Barcelona suffered their second defeat in three matches in La Liga on Saturday, with Michael Krohn-Dehli scoring and setting up another goal in a 2-1 victory for Sevilla.
Neymar's double helped Barcelona cruise to a 5-0 victory in the first leg of their King's Cup last 16 tie against Elche.
News of all that's transpired on and off the football field
News of all that's transpired on and off the football field
With the distraction of two individual scoring records safely out of the way, Barcelona forward Lionel Messi can turn his full focus on helping the club win the major silverware that eluded them last season.
Hegerberg hat-trick fires Lyon to fourth straight Champions League
News of all that's transpired on and off the football field
Cristiano Ronaldo took his tally for the La Liga season to a phenomenal 13 goals in six appearances with his third treble of the campaign as Real Madrid romped to a 5-0 win at home to Athletic Bilbao on Sunday.
Seven-times champions AC Milan, knocked out of the Champions League by Barcelona in the last two seasons, were drawn against the Catalans again in the group stage of this season's competition on Friday.
Cristiano Ronaldo admits that he suffered for pushing himself too much at the end of last season but is now close to his best as Real Madrid prepare to face Real Sociedad this weekend.
New Valencia coach Gary Neville remains without a La Liga win after his side twice recovered from a goal down to rescue a fortunate 2-2 draw at home to Getafe on Saturday.
News of all that's transpired on and off the football field.
Barcelona's Lionel Messi, Luis Suarez and Neymar motored past 100 goals for the season.
Atletico Madrid demonstrated their remarkable team spirit to come roaring back from two goals and a man down to draw 2-2 at Liga debutants Girona on Saturday, after Antoine Griezmann had been sent off for the first time in his career.
News of all that's transpired on and off the football field