Los Blancos broke the world transfer record to sign the forward, paying Tottenham €100 million [£86m] to bring the 24-year-old to the Santiago Bernabeu just before the close of the summer transfer window.
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"He's a great player and I have the pleasure of being on the same team as him," the Brazilian enthused. "I haven’t trained with him yet but I’m sure he’ll do well. To be at Real Madrid, you have to!"
Marcelo has been ruled out of the trip to the Madrigal after picking up a thigh problem during the Selecao's 6-0 rout of Australia last weekend, but the defender is confident of making a quick recovery.
"I'm getting better every day and hope to be back from the injury to help Real Madrid as soon as possible," the full-back explained.
"At first we thought it was one thing but it turned out to be less serious and I hope to play again soon."
Madrid's meeting with Villarreal is scheduled to get under way at 21:00BST.