Lukaku struck the opener for Chelsea to give the Blues an early lead before Reece James powered a rocket past Bernd Leno in the 34th minute to seal all three points for the West Londoners.
Arsenal were off to a bright start at the Emirates as Smith Rowe whipped a stinging shot two minutes into the game, forcing a good save from Chelsea goalie Edouard Mendy.
Scot Kieran Tierney came close to scoring for the Gunners but saw his threatening drive down the left snuffed out by the Chelsea defence.
However, it was Chelsea who broke the deadlock in the 14th minute to take the lead. Right-back Reece James squared a pass to Lukaku—one just enough to beat Bernd Leno in the box—before the Belgian striker bundled the ball into the net to send Chelsea in front.
Few minutes later, Gunners newboy Sambi Lokonga whipped a shot from 20 yards but saw his effort go wide.
Although Arsenal tried to press high pushing Chelsea backward a few times in the first half, they were punished minutes later in another Chelsea buildup.
This time it was James who smashed a Chelsea-esque rocket from the box to double the Blues lead before extra time.
Marcos Alonso had collected a return from Havertz in the final third before spraying a pass to Lukaku. The Belgian, who looked clean through to collect the ball before he was felled, managed to roll a pass to Mason Mount who played in an unmarked James into the box.
Then James powered a right-footed shot into the far left corner to send Chelsea clear before the break.
In the second half, it had seem the half-time talk from Arteta injected a new rhythm to the Arsenal players as they pressed with more intent.
They pushed Chelsea back more and came close to scoring when Saka whipped a stinging shot from 23 yards forcing a fantastic save from Mendy.
Chelsea almost made it three after the hour mark when Mount lifted a pass in the path of Lukaku. It could have been a brace for the Belgian on his second debut but his sublime nod, which was palmed away by Bernd Leno, struck the cross bar before it was cleared.
Chelsea registered 22 shots (five on target) against Arsenal's six (three on target) on an evening where they had looked completely in charge from the start of the game.
Chelsea's win on Sunday sent them top of the Premier League table while Arsenal dropped down to the relegation zone.
The Gunners had lost to Brentford (2–0) in what was an embarrassing defeat in their opening game of the campaign before losing to neighbours Chelsea on Sunday evening.
Next, Chelsea will travel to Merseyside to take on second placed Liverpool on 28 August while Arsenal will play away against Manchester City on the same day.
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