Rinsola Babajide gave the Reds an unexpected lead against the reigning champions, but despite a stunning strike from Rachel Furness on the brink of half-time, goals from Jordan Nobbs and Miedema ensured the Gunners took the three points in Chester.
The Gunners started brightly with Liverpool keeper Anke Preuss forced into saving with her feet one minute in from Nobbs, but, against the run of play Babajide’s pace got her away from Louise Quinn and under pressure she kept her feet and calmly slotted past Pauline Peyraud-Magnin.
It was Nobbs who created the equaliser, her cross failed to be cleared and Miedema, who was yet to find the net in 2020 before Thursday evening, finished from six yards off the crossbar.
Minutes later and Nobbs had one of her own, Lisa Evans’ pinpoint cross invited her to power her header into the top corner past Preuss to give the Gunners the lead.
Then just before half time, Evans’ weak back header didn’t reach Peyraud-Magnin and Furness pounced with a stunning volley into the roof of the net.
Arsenal were gifted the first real chance of the second-half but Miedema uncharacteristically fired the ball well over the Liverpool net.
Remarkably that seemed to spark the visitors and the stage was set for a big 20 minutes, Liverpool fans cheering every challenge and Arsenal boss Joe Montemurro getting more frustrated by the minute.
But the winner came for Montemurro’s team via the head of Miedema from Leonie Maier’s superb right-wing cross, making the result a harsh one for a Liverpool team who arguably put in their best performance of the season so far.
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Arsenal's match-winner Vivianne Miedema said: “You obviously start looking at the clock, but then you kind of know there is always going to be that one chance and luckily that came and from there on I didn’t have the feeling that we were going to give it away again.
“I’ve always been complaining that we don’t play enough crosses to my head so I’m very happy that it happened today.
“I think we made it really hard for ourselves in the first half, we didn’t play our football. Liverpool did a good job, they had two chances and they finished them, and then for us coming out after half-time we hoped that one goal will be enough. It seemed to be enough today, but I think we were quite lucky in getting the three points.
“In the first half we didn’t really switch the ball enough and the second half with all the crosses coming in you could see that we created more chances.”
Liverpool goalscorer Rachel Furness said: “I was screaming for what felt like 10 minutes for the ball to be switched but you’ve just got to gamble. I moved up the pitch and I just gambled on her missing it and thankfully I got on the end of it.
“You could say it was a bit of a hit and hope but I connected well and I’m pleased it went in the back of the net.
“I think we’ve taken one of the best teams in Europe all the way and we’ve come off disappointed not to get anything out of the game. That just shows that in the team and in the squad how well we’re doing that we’re disappointed just to get beat by Arsenal. We will look back at it and take the positives out of the game but we’ve got to put them little mistakes right going into Sunday’s game against Chelsea.”
Liverpool (4-2-3-1): Anke Preuss; Leighanne Robe, Niamh Fahey, Sophie Bradley-Auckland ©, Becky Jane; Rachel Furness, Jade Bailey; Mel Lawley, Niamh Charles Kirsty Linnett; Rinsola Babajide.
Substitutes: Rhiannon Roberts for Linnett 67, Ashley Hodson for Charles 78, Jess Clarke for Bailey 85
Substitutes not used: Rylee Foster, Christie Murray, Amy Rodgers, Jemma Purfield
Bookings: Bradley-Auckland 5, Robe 51, Babajide 86
Arsenal (4-2-3-1): Pauline Peyraud-Magnin; Katie McCabe, Louise Quinn, Viktoria Schnaderbeck, Leonie Maier; Danielle van de Donk, Leah Williamson; Jordan Nobbs ©, Lisa Evans, Beth Mead; Vivianne Miedema.
Substitutes: Jennifer Beattie for Mead 54, Melissa Felis for McCabe 88
Substitutes not used: Manuela Zinsberger, Ruby Grant, Ruby Mace
Bookings: Beattie 56, McCabe 61
Referee: R Welch