The diminutive Russian, who scored all four in a 4-4 draw in April, hammered home after 58 minutes to complete a Gunners comeback after a Glen Johnson own goal had cancelled out Dirk Kuyt's first-half strike.
And although they had inferior possession to their hosts, few would begrudge the Gunners the points as they moved up to third in the Premier League.
The Reds welcomed top scorer Fernando Torres back for his first start in six weeks and the Spanish striker seemed to invigorate Liverpool.
However, he failed to find the back of the net early on after a Steven Gerrard pass split the Arsenal defence in two.
Rafael Benitez's men looked a completely different side to the one which suffered a demoralising 2-1 defeat by Fiorentina on Wednesday and it came as no surprise when Kuyt slammed in the 41st minute.
But just as Liverpool looked to settle into a similar routine in the second period, disaster struck as Samir Nasri's cross caught the faintest of touches off Jamie Carragher, hit Johnson and rolled past the wrong-footed Reds keeper Jose Reina.
Within ten minutes the game had turned on its head as Arshavin touched the ball away from Johnson on the edge of the area before firing a trademark bullet-shot into the near corner.
Liverpool weren't about to relinquish the points that easily and barraged forward again but, for all their superior possession, the Reds' attacking threat seemed to have been snubbed out.
Italian Alberto Aquilani was soon introduced and, despite multiple crosses being fired into the Arsenal box, the ball would not fall for Liverpool as they stay seventh in the league - a demoralising 13 points adrift of leaders Chelsea.