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Arsenal lost for the first time since February as Barcelona's Asisat Oshoala haunted her old club in their Women's Champions League Group C opener.
Mariona Caldentey scored the rebound from an Oshoala shot for the first.
Nigerian Oshoala ran down the right wing and squared it for Alexia Putellas to slot home and added a third herself from a sublime Mariona through ball.
Frida Maanum bundled in a consolation for the visitors before Lieke Martens chipped in the fourth for the holders.
Putellas should have made it 5-1 deep into stoppage time but her penalty was saved by Manuela Zinsberger.
Oshoala, 26, played for Arsenal from March 2016 to February 2017, helping them to win the FA Cup, and did not celebrate her goal at the Johan Cruyff Stadium.
It took Arsenal 55 minutes to have a shot, with Vivianne Miedema's weak effort rolling straight to goalkeeper Sandra Panos.
The Gunners did create more chances as the game wore on with Nikita Parris having a shot cleared off the line shortly before Maanum struck.
Jonas Eidevall's Gunners were one of the form teams in Europe coming into the game, with eight wins from eight games in all competitions this season, scoring at least three in each match.
They were unbeaten in 20 games in all competitions, going back to February.
Unfortunately for them, Barcelona had also won all their matches this season - five in the league - and this was the first time they hit fewer than five goals in a game.
European champions Barca showed why they will be tough to stop this season and should definitely have extended that scoring run, ending with 35 shots, 14 on target.
Next in the Champions League, the Gunners host German side Hoffenheim on Thursday, 14 October, with Barcelona going to Denmark to face Koge.
Hoffenheim beat Koge 5-0 in Tuesday's other Group C game.
Line-ups
Barcelona Femenino
Formation 4-3-3
- 1Paños
- 8Torrejón
- 2ParedesBooked at 46mins
- 4León
- 18CrnogorcevicSubstituted forRolföat 77'minutes
- 14Bonmatí
- 12Guijarro
- 11Putellas
- 7Hansen
- 20OshoalaSubstituted forMartensat 71'minutes
- 9CaldenteySubstituted forVilamalaat 83'minutes
Substitutes
- 3Fernández
- 5Serrano
- 6Pina
- 10Hermoso
- 13Coll
- 15Ouahabi
- 16Rolfö
- 17Pereira
- 19Vilamala
- 22Martens
- 23Engen
- 24Font
Arsenal Women
Formation 4-3-3
- 1Zinsberger
- 16Maritz
- 6Williamson
- 5Beattie
- 7Catley
- 13WältiSubstituted forNobbsat 71'minutesBooked at 90mins
- 10LittleSubstituted forIwabuchiat 79'minutes
- 12Maanum
- 9MeadBooked at 51minsSubstituted forHeathat 55'minutes
- 11MiedemaSubstituted forFoordat 56'minutesBooked at 76mins
- 15McCabeBooked at 35minsSubstituted forParrisat 56'minutesBooked at 90mins
Substitutes
- 3Wubben-Moy
- 4Patten
- 8Nobbs
- 14Parris
- 18Williams
- 19Foord
- 22Schnaderbeck
- 23Iwabuchi
- 28Cull
- 77Heath
Live Text
Match ends, Barcelona Femenino 4, Arsenal Women 1.
Second Half ends, Barcelona Femenino 4, Arsenal Women 1.
Nikita Parris (Arsenal Women) is shown the yellow card.
Penalty saved! Alexia Putellas (Barcelona Femenino) fails to capitalise on this great opportunity, right footed shot saved in the bottom right corner.
Jordan Nobbs (Arsenal Women) is shown the yellow card for a bad foul.
Penalty Barcelona Femenino. Alexia Putellas draws a foul in the penalty area.
Penalty conceded by Jordan Nobbs (Arsenal Women) after a foul in the penalty area.
Mapi León (Barcelona Femenino) wins a free kick in the defensive half.
Foul by Caitlin Foord (Arsenal Women).
Sandra Paños (Barcelona Femenino) wins a free kick in the defensive half.
Foul by Nikita Parris (Arsenal Women).
Foul by Patri Guijarro (Barcelona Femenino).
Jordan Nobbs (Arsenal Women) wins a free kick in the defensive half.
Attempt missed. Bruna Vilamala (Barcelona Femenino) header from the centre of the box misses to the right. Assisted by Lieke Martens with a cross.
Attempt saved. Irene Paredes (Barcelona Femenino) right footed shot from the right side of the six yard box is saved in the top centre of the goal. Assisted by Caroline Hansen with a cross.
Corner, Barcelona Femenino. Conceded by Manuela Zinsberger.
Patri Guijarro (Barcelona Femenino) wins a free kick in the defensive half.
Foul by Mana Iwabuchi (Arsenal Women).
Goal! Barcelona Femenino 4, Arsenal Women 1. Lieke Martens (Barcelona Femenino) right footed shot from the centre of the box to the centre of the goal. Assisted by Patri Guijarro with a through ball.
Substitution, Barcelona Femenino. Bruna Vilamala replaces Mariona.
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