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Zinedine Zidane's side joined Atletico Madrid on 66 points and moved top of the table, although Atletico can reclaim first place when they visit Real Betis on Sunday.
Real, who were knocked out in the last 16 by Manchester City last term and Ajax Amsterdam the season before, reached the last eight for the first time since 2018.
Churchill Brothers survived a last-minute scare to beat 10-man Gokulam Kerala FC 3-2 and extend their lead atop the I-League table.
A Luis Suarez header gave Atletico Madrid a 1-0 home win over Getafe in coach Diego Simeone's 500th game in charge.
The Catalans have endured an inconsistent season so far, losing four times already in the league.
Real Madrid captain Sergio Ramos once again proved to be the man for the big occasion as he converted a fiercely debated penalty to help his side to a 3-1 win.
Shakhtar Donetsk pulled off a shock 3-2 win away to 13-time winners Real Madrid in their Group B opener, despite the Ukrainian side missing 10 players due to injuries and COVID-19.
Barcelona fell to their first defeat in La Liga under new coach Ronald Koeman as they lost 1-0 at Getafe, hours after champions Real Madrid slipped to a 1-0 defeat at home to promoted Cadiz.
Italy extended their unbeaten run to 19 games with a 1-1 draw at home to the Netherlands although they were knocked off the top of their Nations League group in the process.
The awards are likely to be announced on 14 October.