On 31 January 2011, David Luiz completed a move to Chelsea for a €25 million transfer fee and subsequently signed a five-and-a-half-year contract. As part of the deal, Chelsea midfielder Nemanja Matić joined Benfica at the end of the season after his transfer spell at Dutch club Vitesse.
David Luiz was present in every squad during the management of Menezes and was called up to the squad for the Copa América in 2011, but did not make a single appearance at the tournament due to injury. In a friendly with Mexico in October of that year, he scored an own goal, but the Seleção eventually won it 2–1.
Although primarily a centre back, David Luiz can also be deployed as a defensive midfielder or as a full back, and has drawn praise for his physical strength, work-rate, technique, and range of distribution as a defender, as well as his personality, composure in possession, and confidence on the ball, which enables him to play the ball out from the back or launch an attack with long balls after winning back possession. A powerful striker of the ball from distance, Luiz has also been known to take and score from long-range free kicks, which led Tim Vickery to liken him to compatriot Lúcio in 2011. Although in the past he has been criticised in the media for his inconsistent defensive performances, and for being reckless in his challenges, as well as prone to errors or lapses in concentration, during the 2016–17 season, he showed notable improvements upon his return to Chelsea, when the club's new manager Antonio Conte decided to deploy him as a ball-playing centre back in a three-man back-line in the team's 3–4–3 formation. Luiz excelled in the new role, while Conte praised the defender for working to improve his composure and concentration, and singled out Luiz as being "crucial" to the team's success, also labelling him as one of the best defenders in the world.