Before a women’s world record crowd of 91,648 at the Camp Nou, Aitana Bonmati set the tone after two minutes of an opening period in which Barcelona repeatedly caught Wolfsburg flat footed.
Barcelona scored 146 goals in 27 matches as they won the Spanish league title and had hit 32 in the Champions League, but they had not scored in four previous meetings with Wolfsburg.
Bonmati quickly changed that. Left back Fridolina Rolfo lofted a free kick from deep in the Barcelona half into the gap behind the Wolfsburg centre backs, as they turned ponderously and uncertainly, Bonmati scampered past and tucked the ball home.
Caroline Graham Hansen added a second after 10 minutes. Ana-Maria Crnogorcevic stole the ball and played it into the Norwegian who had plenty of time to pick her finish.
In the 33rd minute, Marta Torrejon cut in from the right and once again was allowed time to choose between team-mates in front of goal, cutting the ball back to Jennifer Hermoso, who curled a shot into the far corner.
Inevitably, Ballon d’Or winner Alexia Putellas joined the scorers, outpacing and out-muscling the centre-backs as she ran on to a through ball and shot through goalie Almuth Schult.
Crnogorcevic had a close range strike disallowed for offside at the start of the second half and even though Barcelona continued to create chances, their finishing touch was less sure as Schult pulled off a string of saves.
Jill Roord gave Wolfsburg hope as she broke through to score after 73 minutes
But Putellas restored the four-goal lead with five minutes to play. She broke into the box and drew a clumsy challenge from Wolfsburg skipper Dominique Janssen. Then rolled the penalty into the corer of the net.
The attendance broke the record of 91,553 set three weeks ago at the Camp Nou as Barcelona beat Real Madrid in the quarter-finals.
Barcelona had 20 shots on target over the match while the Bundesliga leaders managed just three.