The league leaders suffered just their second loss of the league season after second-half finishes from Gabriel Martinelli and Leandro Trossard at Emirates Stadium.
The Reds had fallen behind first in the contest when Bukayo Saka scored after 17 minutes but drew level in first-half stoppage time courtesy of an own goal from Gabriel.
Martinelli put the hosts back in front in the 67th minute as Trossard then wrapped up the win towards the end after the visitors were reduced to 10 men following the sending-off of Ibrahima Konate for a second bookable offence.
Team news
Trent Alexander-Arnold made his first start since the Emirates FA Cup meeting between the sides last month after fully recovering from a knee injury.
Cody Gakpo and Ryan Gravenberch were the other alterations to the line-up that defeated Chelsea in midweek.
Alisson, Gomez (Thiago, 85), Van Dijk, Konate, Diaz, Mac Allister, Jones, Gakpo (Nunez, 58), Jota, Gravenberch (Elliott, 58), Alexander-Arnold (Robertson, 58).
Unused subs: Adrian, Kelleher, Clark, McConnell, Quansah.
First half
There was an end-to-end start to the contest that saw both teams work opportunities in front of goal.
Diogo Jota and Gakpo threatened for Liverpool, while Saka headed wide from inside the six-yard box off a counter prior to him opening the scoring.
Kai Havertz was sent through on goal by Martin Odegaard’s clip over the top. Alisson Becker saved the German’s eventual finish but the rebound fell kindly to Saka, who smashed the hosts into the lead.
The Reds’ response was somewhat encouraging, Alexander-Arnold delivering a threatening ball into the box that Gakpo nearly directed towards goal as Virgil van Dijk then went close from a corner.
Meanwhile, Gabriel was involved at both ends towards the end of the first half. After curling a shot that was kept out by Alisson in the aftermath of a free-kick, the Arsenal centre-half inadvertently put the ball into his own net to make the game 1-1.
Luis Diaz persisted when William Saliba looked to shepherd Gravenberch’s pass into the arms of goalkeeper David Raya. The Colombian found a way to get a toe onto the ball that ended up striking the hand of Gabriel and trickling in.
Second half
Liverpool flew out of the blocks after the break and Curtis Jones was inches away from putting his side into the lead with a curler that had beaten Raya.
Arsenal grew back into the action, which now had a more even feel. Their appeals for a penalty were turned down when Alexis Mac Allister halted Martinelli’s charge into the box.
But they were able to restore their advantage midway through the second period.
A long ball over the top caused a defensive mix-up between Van Dijk and the onrushing Alisson, allowing Martinelli, who was in position to take advantage, the simplest of finishes into an empty net.
Jakub Kiwior squandered a golden chance to establish a two-goal lead for the Gunners, heading straight at Alisson when free in the box. The Reds immediately sprung a counter-attack but Darwin Nunez fired over from a tight angle.
A positive for the visitors was Thiago Alcantara emerging from the bench for his first appearance of the season but they would finish the game a man down after Konate’s dismissal.
A disappointing afternoon was then capped off in minute 93 as Trossard’s hit from inside the area took a nick off Van Dijk and ended up beating Alisson.
