Rotherham slumped to a second home defeat in succession, thanks to Ricky Ravenhill's second-half strike.
Rotherham were the brighter team early on and Mark Burchill, Dale Tonge and Micky Cummins all had decent efforts.
But Darlington almost took a first-half lead when Liam Hatch's piledriver of a shot hit the post.
The visitors broke the deadlock on 62 minutes when Rotherham squandered several chances to clear and Ricky Ravenhill prodded home from six yards.
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Darlington: Brown, Austin, White, Foster, Valentine, Purdie, Ravenhill, Kennedy, Burgmeier (Miller 90), Clarke (Hulbert 84), Hatch (Blundell 54). Subs Not Used: Proudlock, Kazimierczak.
Goals: Ravenhill 61.
Att: 3,322
Ref: Tony Bates (Staffordshire).
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