The Chelsea defender was strongly linked with the Spanish side over the summer.
Reports claim Barcelona were prepared to pay £65million to bring the defender to Camp Nou.
Luiz told Gazeta Esportiva: “There was an official proposal [from Barcelona], but I opted for Chelsea. It was better for me and better for everyone.
“I am happy to be at a big club and be in the national team representing my country.”
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Liverpool have unveiled their new home kit for next season, sticking with the hugely popular retro styling of the current shirt.
The reputation of the Premier League means it is the most popular and one of the most watched leagues in the world.