Benzema's league-leading 12th goal allowed Madrid to extend their winning streak to seven matches in all competitions and increase their lead at the top of the league standings.
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Spanish league leaders Real Madrid can increase their advantage at the top when they host Athletic Bilbao in a match postponed from the ninth round.
Marco Asensio, Nacho Fernández, Vinícius Júnior and Ferland Mendy all scored to give Madrid its fourth straight straight victory in all competitions.
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Real Madrid forward Karim Benzema wasn't present Wednesday for the opening of his three-day trial for involvement in an alleged attempt to blackmail former France teammate Mathieu Valbuena over a sex tape.
Carlo Ancelotti's men travel to Ukraine after their La Liga game at home to Athletic Bilbao was postponed to allow their South American players more time to recover after the international break.
Sébastien Thill scored a 90th-minute winner as the newcomers stunned Real Madrid 2-1 at the Santiago Bernabéu Stadium on Tuesday.
UEFA has been forced to abandon its attempt to ban Super League clubs Barcelona, Juventus and Real Madrid from the Champions League due to court action over UEFA's attempt to punish the rebellion.
The draw on Saturday gave Madrid a three-point lead over Sevilla at the top of the table.
Carlo Ancelotti's team has scored 21 goals so far this season led by a superb Karim Benzema, who has scored eight and assisted in seven.
It was Madrid's fourth straight league win, taking Carlo Ancelotti's team back to the top of the standings with 16 points from six matches, two points ahead of defending champion Atletico Madrid.
The first of three consecutive matches in the Santiago Bernabeu sees Carlo Ancelotti's side look to build on their positive start to the season.
Vinicius Jr levelled for Madrid in the 86th minute with his shot also taking a big deflection to wrong-foot Valencia keeper Giorgi Mamardas.
Club Brugge defence as it must cope with Paris Saint-Germain's attacking armada of Lionel Messi, Neymar and Kylian Mbappe.
Madrid fans were frustrated with the failed negotiations to bring in Mbappe at the transfer deadline last month, but a few matches into the new season they have found that they can count on Vinicius.
Madrid fans were frustrated with the failed negotiations to bring in Mbappé at the transfer deadline last month, but a few matches into the new season they have found that they can count on Vinícius Júnior.
The game marked Madrid's return to the Santiago Bernabeu Stadium more than 18 months after it was closed because of the coronavirus pandemic and a massive renovation project.
Madrid will get to play at its venue when it hosts Celta Vigo in the Spanish league on Sunday, 560 days after it last hosted a match at the stadium.
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