The visit by Madrid will close a three-game home stretch for Barcelona that coach Ronald Koeman called crucial to getting his team back on the winning path.
The charges are punishable by up to five years in prison and a 75,000 euro fine. Benzema has denied wrongdoing.
Vinicius scored in 51st and 56th minutes while Rodrygo (64th), Karim Benzema (90+1) and an own goal from Shakhtar captain Sergiy Kryvtsov helped Madrid.
Espanyol's victory comes few days after they shocked La Liga leaders Real Madrid 2-1. Cadiz extended their winless streak to four matches.
A visit from Valencia on Sunday kicks off a three-game home stint that the Barcelona coach Ronald Koeman said must mark a turnaround for his beleaguered team.
After a near-perfect start to the season, Real Madrid are three consecutive games without a win in all competitions. Sunday's results also dropped Barcelona to ninth in La Liga.
In other matches across Europe, Real Madrid will pay a visit to Espanyol in La Liga while Paris Saint-Germain are looking for ninth straight win in Ligue 1.
The result means that Sheriff Tiraspol become just the second club to win on their first Champions League trip to the Bernabeu, after Arsenal in 2005-06.
The move could eventually lead to disciplinary action restarting against the rebel clubs after it was abandoned on Monday night.
The UEFA Appeals Body has declared today the proceedings against Real Madrid, Barcelona and Juventus null and void as if it had never been opened.
This is the first time this season Real Madrid have been held scoreless after outscoring opponents 22-8 in its first seven matches in all competitions.
Camavinga was Madrid's only signing at the transfer window's deadline, arriving amid the disappointment of the club's failed attempt to bring in his France teammate Mbappe.
Benzema scored twice to reach his double century feat. Real Madrid were also helped by a hat-trick from Marco Asensio on Wednesday in La Liga.
The three clubs are facing a ban from the Champions League for refusing to renounce the Super League project.
With this victory, Real Madrid lead the La Liga standings with 13 points, two more than defending champions Atletico Madrid,
Debutant Sheriff Tiraspol won 2-0 against Shakhtar Donetsk in UEFA Champions League 2021. English clubs Liverpool and Manchester City too recorded victories.
The Brazilian had been often criticized for his lack of goals but has clearly improved, becoming an even greater threat as he continues to display amazing speed and uncanny skills.
With goals by Vinicius Junior and debutant Eduardo Camavinga and Karim Benzema, Real Madrid twice came from behind before comfortably beating Celta Vigo 5-2
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