The visitors were on top in the opening exchanges and almost opened the scoring in the eighth minute. Dani Parejo clipped the free-kick over the top for Rodrigo's run on the left, who was unmarked and fired the ball across the face of goal, but Ezequeil Garay could only guide his effort over the bar from six yards out.
Valencia took a deserved lead in the 11th minute. Parejo delivered a corner deep to the back post. Rodrigo was there to head the ball back across the face of goal where Mouctar Diakhaby rose highest to nod the ball into the net from six yards.
Soon after, Jose Luis Gaya offloaded the ball towards Parejo on the edge of the box and he hit a low strike towards the bottom corner. Petr Cech made a fine stop, but the rebound remained in the box. Ainsley Maitland-Niles tried to head the ball back to his keeper, but Goncalo Guedes closed him down and tried a first-time effort, only to guide his attempt over the bar.
The hosts levelled matters in the 18th minute. Alexandre Lacazette released Pierre-Emerick Aubameyang through the middle and the striker surged into the box who cut back inside past his marker and offloaded towards Lacazette on the charge, who had an open goal to slide his left-footed strike into the back of the net.
Seven minutes later, the Gunners took the lead. Granit Xhaka lifted a dangerous cross into the box from the left flank with Lacazette getting the better of his man in the middle and heading the ball down towards the bottom corner. Neto pushed the ball against the post, but it struck the inside of the woodwork and travelled backwards over the line.
Unai Emery's side almost made it three just after the half-hour mark. Xhaka's cross to the back-post found an unmarked Aubameyang, who took the strike first time, drilling his volley into the ground, but the ball bounced comfortably over the bar.
It was a tepid start to the half from both sides. Valencia had a half-chance five minutes after the break. Arsenal cleared their lines from a corner into the box. However, Carlos Soler went for the strike from distance. His effort appeared to be heading towards the target before it came off Diakhaby and went out for a goal-kick.
With just over an hour gone, Aubameyang opened up the Valencia defence down the left flank and he supplied a fine cross into the middle. Facundo Roncaglia failed to clear the ball, leaving Lacazette unmarked in the six-yard box. However, the Frenchman could connect with his header and it allowed Gaya to make the clearance.
Lacazette had another excellent chance to grab his hat-trick soon afterwards. Xhaka lined up a strike from the edge of the box that was deflected into the path of the forward in the left inside channel. He took a touch before firing towards the near post with his strike, but Neto made the save with his feet. Lacazette went for the rebound, only to see his second attempt repelled by Gabriel Paulista.
With ten minutes to go, Valencia threatened down the right through Daniel Wass and he cut the ball back into the middle. Fellow substitute Kevin Gameiro gathered, flicking the ball up before going for goal, but he blasted his attempt over the bar.
The Gunners secured the crucial third goal in injury time. Lacazette's deflected shot brought a good save out of Neto. The ball rebounded to Sead Kolasinac, who lifted the ball to the back post for Aubameyang to ghost in and volley home from a tight angle for a two-goal lead heading in to the return leg at the Mestalla next week.
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