The hosts took the lead in the fifth minute then doubled it with ten to play and, although Cauley Woodrow replied from the penalty spot, Albion scored another to secure the win.
The Reds are still in the second automatic promotion place in League One, but only on goal difference ahead of Sunderland who have two games in hand and scored an 89th-minute winner at Rochdale. Fourth-placed Portsmouth also won and are just two points behind Barnsley with a game in hand.
Daniel Pinillos replaced Ben Williams at left-back in the only change from the side that drew 2-2 at home to Coventry City last week.
The hosts took the lead in the fifth minute when Marcus Harness ran down the left wing and passed to Scott Fraser whose shot from the edge of the box was saved by Adam Davies but went straight to Jamie Allen who tapped into the empty net from five yards.
Barnsley had long-range shots from Pinillos and Cameron McGeehan easily saved but the hosts had much the better of the first 15 minutes. Liam Boyce was booked for diving when he thought he won a penalty, seconds after a possible handball by Alex Mowatt in the area, while Allen’s dipping volley from 25 yards went just inches over.
The Reds got back into the game and were on top for the rest of the half without being at their best. Jacob Brown’s glancing header from a Dimitri Cavare cross was straight at goalkeeper Bradley Collins then the same player went clean through on goal but miscontrolled and was tackled.
Mamadou Thiam blazed well over from just outside the box after an excellent move involving Cauley Woodrow and McGeehan. Barnsley also thought they should have had a penalty after a Burton defender appeared to block a cross with his arm.
The hosts had a huge chance to double their lead three minutes into the second half when Lucas Akins’ overhead kick put Boyce clean through but he tried to dink the ball over Davies and his weak effort was easily caught by the goalkeeper.
After a poor first 15 minutes of the second half, Daniel Stendel brought Mike Bahre and Callum Styles on for Thiam and Brown as Barnsley reverted to 4-5-1.
Burton then missed another massive chance as Harness controlled an Akins cross from the right wing and nutmegged Liam Lindsay but, eight yards out with only Davies to beat, he shot wide of the bottom left corner.
That seemed to spark Barnsley into life. Hedges had the visitors’ first shot on target of the second half but his swerving 20-yard effort was beaten away by the goalkeeper then Styles shot wide from a similar distance and Cavare had a shot blocked by a defender deep inside the box. Woodrow headed a Hedges corner just over the crossbar on 73 minutes.
It was 2-0 Boyce beat the offside trap and went clean through on goal then smashed past Davies from the edge of the box. Barnsley replied five minutes later when they were given a penalty for what looked like a high foot and Woodrow fired in his 16th goal of the season.
Burton made it 3-1 in the 90th minute when the ball was worked to Boyce on the left of the box and he squared to the unmarked Harness who fired past Davies from close range.
Barnsley (4-4-2): Davies; Cavare, Pinnock, Lindsay, Pinillos (Adeboyejo 82mins); Brown (Styles 59), Mowatt, McGeehan, Hedges; Thiam (Bahre 59), Woodrow. Subs: Walton, Jackson, J Williams, B Williams. Yellow cards: Bahre, Woodrow. Goals: Woodrow 85 (pen).
Burton (4-4-2): Collins; Brayford, Buxton, McFadzean, Daniel; Fraser (Fox 78mins), Allen (Wallace 90), Quinn, Harness; Akins, Boyce (Miller 90+3). Subs: Bywater, Bradley, Hutchinson, Clarke. Yellow cards: Boyce. Goals: Allen 5, Boyce 81, Harness 89.
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