A quarterfinal finish will ensure qualification for the Tokyo Olympics for India, which has never made it as a team in Olympic history.
It was Sharath Kamal and Harmeet Desai who helped India to get a winning start, beating Gilles Michely and Eric Glod 11-9, 16-14, 11-6 in the opening doubles.
India's highest ranked paddler G. Sathiyan then lost the first two games in the singles match against Luka Mladenovic before fighting back to prevail 8-11, 9-11, 11-3, 13-11, 11-6.
Sharath then conceded a game to Glod but eventually won 11-3, 11-3, 12-14, 11-5 to complete a 3-0 victory.
Slovenia beat Iran 3-1 in their round of 32 match and will now take on India.
"The Slovenia game will be 50-50. We have to give our best," Sathiyan told .
The Indian women too are a win away from creating history and making their maiden appearance at the Olympic level.
They beat Sweden 3-2 after Archana Kamath beat Linda Bergstrom in the fifth and deciding rubber. She won 11-8, 8-11, 9-11, 11-7, 13-11.
Earlier, top-ranked Indian Manika Batra won both her singles matches, prevailing over Bergstrom and Christina Kallberg 3-1 and 3-2, respectively.
India will now have to get past Romania in the pre-quarterfinals on Friday.
( With inputs from IANS )