Doncaster captain Brian Stock produced a superb 30-yard strike to give his side a victory that lifted them off the foot of the Championship table.
Rovers controlled possession but lacked a cutting edge until Stock picked up a loose ball and unleashed an unstoppable drive that went in off the crossbar.
A Neil Sullivan reflex save denied Paul Gallagher equalising from six yards.
Matt Mills headed over for the hosts before James Coppinger hesitated when clean through to waste another chance.
Doncaster manager Sean O'Driscoll: "Five games unbeaten in this division is a very good achievement.
"We had been on a poor run but we played some good stuff during that time and now things are turning.
"We have a good set of lads who want to do well. We just have to maintain it."
Plymouth manager Paul Sturrockl: "I thought there was a real lethargy to our play today. And I'm a bit disappointed with that.
"I think there has been a mental thought process that we just had to turn up because of the run we were on.
"Most of the fans expected rich rewards from it and it is a mental approach that I think leaked through to the team and duly we have been spanked."
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