A first half goal from Carlton Morris was enough to give 10-men Rotherham all three points against Stanley.
Morris, on loan from Norwich, headed home on the half hour while the Millers had Chiedozie Ogbene sent off eight minutes from time.
Despite piling on the pressure and several goalmouth scrambles, the Reds couldn’t grab an equaliser and it was agony for John Coleman’s men who have now gone four league games without a win.
Rotherham, relegated from the Championship last season, started well and forced Dimi Evtimov into a strong save in the opening seconds from Morris.
Stanley grew into the game and launched a few breaks and set-pieces without testing keeper Daniel Iversen.
The match was even with chances limited until the Millers took the lead on 30 minutes.
They won a free kick on the right of the area, Ben Wiles fired it in and Morris was there to leap above the Stanley defence and head home.
Keeper Evtimov was then shown a yellow card after charging out and tackling former Red Matt Crooks and Rotherham’s Clark Robertson was also booked for a foul on Dion Charles as the game got heated.
Morris almost had a second on the stroke of half-time but his curling effort was just wide.
Coleman brought on winger Sean McConville at half-time as Stanley looked to get back in it.
The Reds were more of a threat after the break with Jordan Clark putting in a dangerous ball which no one was able to get on the end of while, at the back, Ross Sykes made a number of timely tackles.
Robertson glanced a header wide for the home side while, on 56 minutes, Stanley had a great chance through a McConville near post header from a Charles cross which took a deflection and was inches off-target.
Evtimov denied Wiles while Sam Finley was unlucky to see his strike sail just over the bar on 68 minutes and he had another long range blast just off-target four minutes later.
The game was finely balanced and striker Colby Bishop came on for the last 15 minutes.
Stanley had a one-man advantage for the last eight minutes as Rotherham were reduced to ten-men when winger Ogbene was sent off for a second bookable offence.
McConville was desperately unlucky to see a 20-yard strike go just wide and there was a goalmouth scramble near the end with Clark and Seamus Conneely having a go but unable to find a way through.
Charles also was narrowly off-target as Stanley were unable to grab an equaliser.