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Martin Butler's strike just before the hour was enough to settle a game mostly played in driving rain.
Chesterfield huffed and puffed but rarely troubled the visitors who claimed three well deserved points to send their hundreds of soaking supporters home happy.
The Spireites' best spell came in the opening 25 minutes when Paul Hall fired into the side netting and Tcham N'Toya-Zoa was barevly denied by Neil Cutler when through on goal.
But Rotherham slowly took control and Lee Williamson's sidefooted effort against the bar on 39 minutes was a sign of what was to come after the break.
Hartford's men continued their dominance following the restart and made a decisive breakthrough the game's only real moment of quality.
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Butler and Deon Burton both came close to extending United's lead before sub Colin Larkin missed a sitter to level for the home side on 83 minutes.
Williamson went down under a heavy challenge from Derek Niven and with the Millers defenders expecting ref Graham Lows whistle, Larkin broke free but fired badly wide.
It would have been harsh on the Yorkshire side but they played out the remaining minutes comfortably to kick start their season at the third attempt.