The Terriers' 100 per cent start to the League One campaign came to a crashing halt with three red cards issued against them.
Head coach Michael Duff, goalkeeper coach Andy Quy and striker Danny Ward were all dismissed by referee Sebastian Stockbridge.
Duff was dismissed after the final whistle for remonstrating with the referee and Quy for assisting with time wasting.
Mallik Wilks netted a late winner to get Rotherham up and running.
Huddersfield had goalkeeper Lee Nicholls to thank for keeping Rotherham out twice early on.
He denied Sam Nombe on the angle and then did even better to thwart Jonson Clarke-Harris's effort from close-range.
The visitors then had chances of their own, with Tom Lees guilty of missing the easiest as he headed off target at the back post.
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