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Leading scorer Butler plundered his first goal since February to gave Ronnie Moore's strugglers the lead after 30 minutes.
And despite a second-half onslaught from Craig Brown's play-off hopefuls the Millers hung on for only their second home win since December 2.
Butler could have given his side the lead with a header in a high-energy start but for an acrobatic stop from Jonathan Gould after a Chris Sedgwick cross.
And Andy Monkhouse came close when raced onto Robbie Stockdale's deft flick but for a timely intervention by Michael Jackson.
Preston striker Richard Cresswell found his feet and came close to breaking his goal drought, but his first-time shot was high after good work Paul McKenna.
Two minutes later only a superb diving save from Mike Pollitt denied Cresswell with a fierce drive before Phil Gilchrist tidied up.
Rotherham's breakthrough came from a set piece after 30 minutes. John Mullin's ball into the area was headed clear by Jackson but Monkhouse lashed a dipping volley that Gould matched with a super stop.
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He could only parry the powerful effort and Martin Butler was hovering to head in his 11th goal of the seasonThe setback re-ignited Preston's challenge and Cresswell was at the forefront again but Pollitt made another important save.
Minutes after the restart Briscoe tried to catch Rotherham on the hop with a quickly taken free-kick but was Pollitt was alert enough to get behind the low shot.
Dickson Etuhu should have levelled in the 53rd minute but hit a tame shot at Pollitt and the Millers clung on to take the points.