Former Bradford City and Grimsby Town striker Ross Hannah marked his first league appearance for Main with a brace of goals either side of the break.
Declan Slater was also on target and ex-Armthorpe Walfare forward Adam Baskerville rounded off the scoring.
Rossington reached the NCEL Division One play-offs last season after finishing the regular season in fifth – their highest ever league finish.
Ben Hunter’s side host league newcomers Horbury Town on Saturday.
Former West Yorkshire League outfit Horbury opened their campaign with a 5-0 win at home to Ollerton Town.
Lee Morris’ new-look Armthorpe Welfare team got their season off to a poor start, going down 3-1 at home to Dronfield Town.
Dronfield took the lead on 39 minutes when a throw-in found its way to Danny Wood who converted from inside the area.
Jack Mawson fired a low shot into the bottom corner from 15 yards to level the scores after 49 minutes.
However, just over two minutes later Dronfield were back in front when another throw-in found the head of Callum Mawbey and his flicked header looped just inside the far post.
A long ball out of defence then sent Sam Terry sprinting clear to stab the ball home and put the game beyond Welfare.
Armthorpe travel to Worsbrough Bridge Athletic tonight and host Harrogate Railway Athletic next Wednesday.