For the first time this season, and under Grant McCann, the lack of a killer instinct cost Doncaster Rovers.
Rovers had more possession and more attempts at the Pirelli Stadium but Liam Boyce's 47th minute goal consigned them to their first defeat of the season.
They grew into the contest and John Marquis was guilty of missing a sitter on the half hour.
Burton made them pay when Boyce found space just after the interval to break the deadlock.
Doncaster, who went into the game having scored eight goals from their opening three games, enjoyed the better of the second period but just could not find a way past their former goalkeeper Stephen Bywater.
Rovers were not firing on all cylinders during the first period but became more of an attacking threat as the half went on - and they should have lead at the interval.
Marquis, who had earlier seen a header cleared off the line by Kyle McFadzean, missed a gilt-edged chance on the half hour after Rovers sliced Burton open.
Herbie Kane put it on a plate for the striker but he missed the target with the goal at his mercy.
The home side had started brightly and looked a threat in and around the box. Marvin Sordell almost punished some slack play from Andy Butler but fired wide from distance.
Albion's chief threat was midfielder Joe Sbarra who threatened to unlock Doncaster and struck two shots wide before being forced off with an injury just before the break.
Rovers were caught cold following the re-start and found themselves behind in a game for the first time this season after 47 minutes when Scott Fraser played in Boyce whose smart finish across Marko Marosi went in off the post.
The visitors responded well and were almost immediately level but Joe Wright headed a lovely cross from Danny Andrew inches wide.
Mallik Wilks twice got in behind but saw his attempts deflected wide, while Marquis was off target with a snapshot. At the other end David Templeton went close with a curling freekick from just outside the box.
Rovers continued to probe for an equaliser but lacked composure where it counts. Paul Taylor saw his deflected freekick swallowed up by Bywater, while Matty Blair saw an ambitious attempt from distance drift wide.
Burton: Bywater, Brayford, Buxton, McFadzean, Turner, Fraser, Sbarra (Templeton 41), Fox, Akins, Sordell, Boyce (Harness 90). Subs not used: Campbell, Hutchinson, Hodge.
Rovers: Marosi, Mason, Wright, Butler, Andrew, Whiteman, Rowe, Kane (Blair 59), Coppinger (Taylor 59), Wilks (May 81), Marquis. Subs not used: Lawlor, McCullough, Anderson, Beestin.
Referee: Peter Bankes