The Gowfers having lost just once in 15 games, racking up 60 goals.
Rossvale could face a home tie with Glasgow giants Pollok if their Premier Division rivals come through their second round tie at Irvine Vics, which was controversially abandoned last Saturday.
Vale faced Pollok as a lower league club in the competition three years ago, losing 3-0, but have since joined them in the top flight.
The sides have already met twice in the league this season, Pollok winning 6-1 at Petershill in August and 1-0 at Newlandsfield in September.
The tie may well be switched to a Friday night as Petershill have also been drawn at home, to Benburb.
Glasgow Perthshire are also at home, to former winners Arthurlie, but Ashfield have an away tie at Vale of Leven.
Matches will be played on the weekend of Saturday, October 23.