The Catalan club were strongly linked with a move for the Brazil international throughout the close-season after he was reported to be considered surplus to requirements by returning boss Jose Mourinho.
However, Luiz has now claimed that he only wanted to stay at Stamford Bridge, despite receiving an offer from Gerardo Martino's side.
He 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."
Luiz helped Chelsea win the 2011-12 UEFA Champions League in his first full season at the club, and also featured last term as their defence of the crown ended at the group stages.
But with the London club having returned to Europe's premier cup competition this season, the 26-year-old is looking forward to taking part in some testing encounters.
"It (the Champions League) is always a tough competition with great opponents," he added.
"But it is always good to avoid the teams with a history of success in the competition."
Luiz has failed to feature in Mourinho's squad for the first three games of the new Premier League season.
However, he played the entirety of Chelsea's UEFA Super Cup clash last Friday with Bayern Munich, which they lost on penalties following a 2-2 draw.
