Portsmouth and Peterborough will be looking over their shoulders after John Marquis marked his 100th league appearance for Rovers with a super double to sandwich Matty Blair’s close-range strike in the 57th minute.
Argyle – still to win in the league after 10 games – levelled through Ruben Lameiras’s dipping shot from the edge of the area after 40 minutes but only got their second, through Graham Carey’s powerful drive, deep into stoppage time.
Rovers chief Grant McCann said: “We like to set small targets and after this win here we’ve said we would like to be No 1 by the end of the week.
“We go to Accrington on Tuesday. They are a good side but I’ve set the group the goal of being top by the end of the week.
“We’ve got strength in depth and the attitude of the squad is good. We didn’t start very well, which was really disappointing but the subs – Ali Crawford, Alfie Beestin and Alfie May – made an impact and that’s what you want.
“The response in the second half just shows you the character of the group.”
Marquis capped a man-of-the-match performance with a 90th-minute solo goal, rounding goalkeeper Matt Macey before scoring from an acute angle to take his tally to nine for the season.
Marquis had fired Doncaster ahead after 18 minutes, cutting in from the left to unleash an unstoppable angled drive into the far corner.
Plymouth Argyle: Macey, Smith-Brown, Edwards, Peter Grant, Wylde, Fox, Songo’o (Ainsworth 77), Carey, Lameiras (Fletcher 82), Joel Grant (O’Keefe 68), Ladapo. Unused substitutes: Dyson, Letheren, Law, Rooney.
Doncaster Rovers: Marosi, Mason, Wright, Butler, Andrew, Blair, Kane, Jermaine Anderson (Crawford 59), Wilks (Beestin 80), Marquis, Coppinger (May 59). Unused substitutes: Taylor, Lawlor, Tom Anderson, Amos.
Referee: K Johnson (Somerset).