On 31 January 2011, David Luiz completed a move to Chelsea for a fee of €25 million, a five-and-a-half-year contract, with Nemanja Matić joining Benfica at the end of the season after his transfer spell away at Vitesse in the Netherlands.
He made his official Premier League debut on 6 February, replacing José Bosingwa in a 0–1 home loss against Liverpool. Eight days later, he made his first start for Chelsea in a 0–0 draw against Fulham at Craven Cottage.
Instantly becoming a cult hero amongst the Chelsea fans, David Luiz was awarded the Barclays Man of the Match award for his performance, despite giving away a penalty in the 93rd minute of the game, which was saved by Petr Čech.
On 1 March, David Luiz scored his first goal for Chelsea to help the Blues come from behind to win 2–1 against Manchester United at Stamford Bridge.
On 20 March, he headed in his second goal for the Blues for a 2–0 home win over Manchester City, and again receiving the man of the match award, as well as the Player of the Month for March.
David Luiz missed the first three games of 2011–12 season due to a knee injury. He made his return to the first team on 13 September in a Champions League group stage match against Bayer Leverkusen, and he scored from 15 yards to break the deadlock in an eventual 2–0 home win.
On his second match, a League Cup third round tie against Fulham, he netted his penalty shoot-out attempt in a 4–3 win (0–0 after 120 minutes).
On 5 February 2012, in a league home fixture against Manchester United, David Luiz put Chelsea ahead 3–0 in the 50th minute after his header was deflected by Rio Ferdinand, following a Juan Mata free kick. The match ended with a 3–3 draw.
On 25 February, through a curled shot, he opened the score against Bolton Wanderers in an eventual 3–0 at home.
On 14 March, Chelsea faced Napoli in the Champions League’s round of 16, following a 3–1 loss at the Stadio San Paolo in Naples. David Luiz made a stunning performance to help his team win the tie with a 4–1 extra-time win, being subsequently chosen by UEFA as the man of the match, an accolade he also received in the first leg of the quarter-finals against former team Benfica in a 0–1 away win.
However, after leaving the pitch in the FA Cup semi-finals against Tottenham with a muscular injury, it was announced that he would miss both of the Champions League semi-finals encounters against Barcelona and the domestic cup final.
He played, however, in the Champions League final – John Terry was also suspended for the match – David Luiz appeared, and started for Chelsea, playing the full 120 minutes, along with converting his penalty shootout attempt as the Blues won the shootout 4–3.
On 22 September 2012, David Luiz signed a new five-year contract with Chelsea. He started the new season again as a regular alongside either Gary Cahill or Terry, and scored his first goal from a free-kick against Nordsjælland in a 0–4 away win for the campaign’s Champions League.
In the Club World Cup in 2012, in which Chelsea lost in the final to Corinthians, he was chosen the second best player of the tournament, receiving the Silver Ball for his performances, one of which was as a defensive midfielder.
He played in that position in an 8–0 home thrashing of Aston Villa the following week, being chosen man of the Match and netting the second from a free-kick.
On 17 April 2013, David Luiz scored during a 3–0 victory against London rivals Fulham. He also scored in both legs of the Europa League semi-finals against Basel; the first was a last minute, low free-kick curled around the wall and into the goalkeeper’s bottom left-hand corner to secure a dramatic 2–1 away win, giving Chelsea an advantage going into the second leg at Stamford Bridge.
David Luiz was widely criticized for a controversial incident during Chelsea’s 0–1 away win over Manchester United at Old Trafford on 5 May. After he elbowed opponent Rafael, the United defender kicked out at him and was sent off.
David Luiz, however, was seen smiling while lying on the ground before writhing around in mock agony. David Luiz defended himself, saying he was smiling at the Manchester United fans who could be seen screaming insults and laughing at him.
Return to Chelsea
On 31 August 2016, David Luiz returned to Chelsea from PSG, for a reported fee of £34 million, and signed a three-year deal. On 16 September 2016, he made his return debut at home in 2–1 defeat against Liverpool after John Terry was ruled out for ten days.
On 31 January 2017, David Luiz scored his first goal for the season from a free kick against Liverpool at Anfield. His goal marked his first Premier League goal since April 2013.
On 20 April 2017, Luiz was named in the PFA Team of the Year for the 2016–17 Premier League season.
On 17 September 2017, Luiz received a straight red after a poor challenge on Sead Kolašinac during a 0–0 draw against Arsenal. Luiz became the third player to be sent-off in the last three meetings between the two London side; with the others being Pedro during the FA Community Shield and Victor Moses during the FA Cup Final.