PHOTOS: Barnsley 2, Burnley FC 0
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The Clarets started the brighter of the two teams and Ross Wallace looked as though he'd presented Eddie Howe's side with a deserved lead in the opening five minutes but his stinging drive from the edge of the box was blocked on the line by Rob Edwards.
But the hosts took the lead in the 22nd minute when Jim O'Brien's dangerous cross to the back post was headed back across goal by Craig Davies before Butterfield ghosted in to stab the ball past Lee Grant from close range.
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Hide AdJay Rodriguez went close to levelling the encounter soon after as he cut in from the left before rifling a shot from the angle of the penalty area against the crossbar.
The home side scuppered any attempts of a Burnley equaliser in the second half courtesy of a stubborn defensive line combined with some lacklustre passing from the Clarets. And Keith Hill's side should have seen their advantage doubled on two occasions; Davies the culprit both times.
Firstly the striker had time and space as he raced towards Grant but he pulled his right-footed shot wide of the far post. Then he was guilty of doing the same when he gambled on a long clearance, raced goal-side of Andre Amougou, only to miss the target once again.
The Clarets pressed but without any conviction in the final third and the killer blow came in the 82nd minute as David Edgar misjudged a header close to the left-hand touchline gifting former Bolton man Vaz Te the opportunity to break in to the penalty area and slot past Grant.
And so the Clarets' poor record at Oakwell continued with a 2-0 defeat. They now face Coventry City at the Ricoh Arena on Saturday.