Barcelona were beaten in last year's final by Lyon after winning the competition in 2021
Fridolina Rolfo scored twice as Barcelona thrashed Roma to secure progression to the Women's Champions League semi-finals.
Rolfo scored either side of Maria Leon's stunning curled strike in front of 54,667 joyous fans at the Nou Camp.
Goals from Asisat Oshoala and Patricia Guijarro put the Catalan side out of sight before Annamaria Serturini's low drive gave Roma a consolation goal.
Barca will meet Chelsea or defending champions Lyon in the last four.
Fresh from scoring the only goal in Barcelona's win over Real Madrid in the league on Saturday, Sweden forward Rolfo latched on to a loose ball which Roma had been unable to properly clear and calmly slotted it into the bottom right corner for the opener.
Then she tapped in from Caroline Graham Hansen's low driving cross after Lioness Keira Walsh had set up Leon's rocket from 25-yards out to put the home side in control.
Oshoala nudged home Barca's fourth just one minute into the second half, tapping in from Aitana Bonmati's cross, before Guijarro's header from a corner sealed their spot in the semi-final.
Buoyed by a passionate crowd in Spain, Barcelona oozed class with Walsh dominating play in the middle of the park and fellow Lioness Lucy Bronze thwarting Roma's attempts to score on the counter.
Having conceded just one goal in their first-leg loss in Italy, Champions League debutants Roma struggled to create meaningful opportunities in Spain and were unable to deal with Barcelona's aggressive style.
Serturini's powerful shot was one of their only highlights, while a sublime save from goalkeeper Camelia Ceasar denied Geyse Ferreira a sixth goal in the final few minutes.
Barcelona have reached the Champions League semi-final stage for five consecutive seasons, going on to reach the final three times and winning the tournament once.
Emma Hayes' Chelsea lead eight-time champions Lyon, who beat Barcelona in last season's final, 1-0 on aggregate and could book their place in the semi-final on Thursday at Stamford Bridge.
- Line-upsMatch StatsLive Text
1Paños15Bronze2Paredes4León Cebrián16Rolfö14Bonmatí21Walsh12Guijarro Gutiérrez10Hansen20Oshoala17Paralluelo
- 1Paños15Bronze2Paredes4León CebriánSubstituted forFernández Velascoat 74'minutesBooked at 90mins16RolföSubstituted forRábanoat 80'minutes14Bonmatí21WalshSubstituted forEngenat 66'minutes12Guijarro Gutiérrez10Hansen20OshoalaBooked at 63minsSubstituted forda Silva Ferreiraat 66'minutes17ParallueloSubstituted forVilamalaat 66'minutes
- 3Codina5Fernández Velasco7Crnogorcevic8Torrejón13Coll Lluch18da Silva Ferreira19Vilamala22Rábano23Engen24Font Oliveras25Ramírez30López Serrano
12Ceasar13Bartoli23Wenninger32Linari2Minami15Serturini10Giugliano14Losada7Alves da Silva9Giacinti11Haavi
- 12Ceasar13BartoliSubstituted forDi Guglielmoat 55'minutes23Wenninger32Linari2Minami15Serturini10Giugliano14LosadaSubstituted forGreggiat 45'minutes7Alves da SilvaSubstituted forCiccottiat 78'minutes9GiacintiSubstituted forKramzarat 74'minutes11HaaviSubstituted forGlionnaat 54'minutes
- 3Di Guglielmo5Cinotti6Landström16Ciccotti18Glionna19Selerud20Greggi27Kollmats33Kramzar52Merolla87Öhrström
Referee:Riem HusseinAttendance:54,667Match StatsHome TeamBarcelona FemeninoAway TeamRoma FemminilePossessionHome70%Away30%ShotsHome22Away6Shots on TargetHome9Away2CornersHome10Away0FoulsHome13Away4Live Text Post update
Match ends, Barcelona Femenino 5, Roma Femminile 1.
Second Half ends, Barcelona Femenino 5, Roma Femminile 1.
Attempt missed. Manuela Giugliano (Roma Femminile) right footed shot from outside the box is just a bit too high from a direct free kick.
Jana Fernández (Barcelona Femenino) is shown the yellow card for a bad foul.
Foul by Jana Fernández (Barcelona Femenino).
Zara Kramzar (Roma Femminile) wins a free kick in the attacking half.
Delay over. They are ready to continue.
Delay in match because of an injury Elena Linari (Roma Femminile).
Foul by Lucy Bronze (Barcelona Femenino).
Elena Linari (Roma Femminile) wins a free kick on the left wing.
Corner, Barcelona Femenino. Conceded by Camelia Ceasar.
Attempt saved. Geyse Ferreira (Barcelona Femenino) right footed shot from the left side of the box is saved in the bottom left corner. Assisted by Patri Guijarro.
Attempt missed. Patri Guijarro (Barcelona Femenino) right footed shot from the left side of the six yard box is just a bit too high following a corner.
Corner, Barcelona Femenino. Conceded by Carina Wenninger.
Foul by Ingrid Engen (Barcelona Femenino).
Giada Greggi (Roma Femminile) wins a free kick in the defensive half.
Attempt saved. Bruna Vilamala (Barcelona Femenino) left footed shot from outside the box is saved in the bottom left corner.
Attempt blocked. Zara Kramzar (Roma Femminile) right footed shot from very close range is blocked. Assisted by Benedetta Glionna.
Substitution, Barcelona Femenino. Nuria Rábano replaces Fridolina Rolfö.
Substitution, Roma Femminile. Claudia Ciccotti replaces Andressa Alves.
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