The Gunners easily accounted for Leuven 3-1 to complete a 7-1 aggregate win on Wednesday.
Alessia Russo netted twice to become the tournament's leading goalscorer with seven.
Alessia Russo opened the scoring and hit the third after Mariona Caldentey's penalty put Arsenal back in front following Leuven's equaliser from Sara Pusztai.
England forward Russo is relishing renewing their rivalry with Chelsea.
"So exciting and a team we are so familiar with," Russo told Disney+.
"When you play Champions League football and get closer towards the final you come up against really tough teams.
"To play Chelsea, an English team, probably something that we are not so used to in the quarter-finals, will be amazing.
"Two top teams coming up against each other for a place in the semi-final. It's unreal."
Both teams are littered with Australian professionals with Caitlin Foord, Kyra Cooney-Cross and Steph Catley donning red while Matildas skipper Sam Kerr and Ellie Carpenter are among the Blues' key players.
North Londoners Arsenal won the tournament in 2007, when it was called the Super Cup, and remains the only English team to do so.
Chelsea reached the final once, in 2021, but were routed 4-0 when Barca won their first title.
Earlier, Madrid set up a Clasico against three-time champions Barcelona by beating Paris FC 2-0 for a 5-2 aggregate victory.
Striker Naomie Feller opened the scoring for Madrid and defender Melween N'Dongala put one through her own net.
Paris's cause was made harder in Madrid when defender Théa Greboval was sent off in the fifth minute for pulling back Feller as she ran through on goal.
In Thursday's second legs, Juventus host two-time champions Wolfsburg with the score 2-2 while Manchester United defend a 3-0 lead at home to Atletico Madrid.
with PA
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