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Odisha FC defeated Bengaluru 1-0 to make it three wins in four matches.
The final will be played at the D Y Patil Stadium in Navi Mumbai on Sunday.
The defeat was another blow to Barca and manager Xavi Hernandez after they were left on the brink of Champions League elimination following a draw with Inter Milan last week.
The home win lifted Inter to second place in Group C on six points, three behind leaders Bayern Munich and three in front of Barcelona.
The Polish striker secured Barca's points in the 20th minute when he sped into the area, made a brilliant cut inside to clear a defender and slotted the ball to the goalkeeper's left.
For Bayern the win could not have come at a better time, following three consecutive draws in the Bundesliga.
Lewandowski, who came on as a substitute after the goal, continued his fine start to life in Spain with Barca's second 25 minutes from time to put the visitors in command.
The Polish striker scored his first goal in competition for Barcelona when he opened the scoring in the first minute.
Barcelona dominated the match with almost 70 per cent of possession and 18 goal attempts to two for Rayo.
Lewandowski, who had 12 months remaining on his Bayern contract, moved to Barcelona in a deal worth 45 million euros and has joined the team on their US pre-season tour.