A Bradley Dack brace and long-range Stewart Downing effort undid the Reds, despite them equalising through Conor Chaplin and Cauley Woodrow, and they are now 16 league games without a win.
The hosts had a 4th-minute penalty shout turned down after Lewis Holtby went down under Aapo Halme’s challenge as Joe Rothwell advanced on goal.
Former Red Adam Armstrong then had the ball in the net with a long-rang effort which found the bottom corner, but the referee had already blown for offside.
Barnsley’s first effort came 18 minutes in, Woodrow firing low from the right after some good work to keep possession by Mike Bahre, who laid the ball off for Toby Sibbick to find the forward. Woodrow’s effort was on target, but didn’t trouble Christian Walton.
The striker had another chance two minutes later after Jacob Brown did well to find some space in the box and play him in, but his strike from the middle of the box was well saved by the Rovers ‘keeper.
Despite a bright start, the Reds went 1-0 down due to a defensive error from Mads Andersen, reinstated to the starting lineup for the first time in a month.
The centre-back, under some pressure on the left side of the pitch, attempted to thread a low pass through to Alex Mowatt but horribly misjudged it.
Lewis Travis picked up the ball and played in Armstrong, who worked his way into the box and squared it for Dack to score into an open net.
Almost immediately afterwards the Reds attempted to make their way back into the game, but Alex Mowatt’s ball into the box couldn’t quite reach Brown.
Dack, Rovers’ top scorer with seven so far in the league, then teed up Sam Gallagher on the 31st minute after Elliott Bennett found the midfielder with a cross, but Gallagher’s powerful effort was wide of the far post.
Woodrow was then called upon to head the ball away after Gallagher turned Andersen with some good dribbling and crossed the ball into the box.
On 43 minutes, Ben Williams – who was one of Barnsley’s better players – denied what looked to be a certain second goal for the hosts, as Dack once again threatened with a low ball into the box from the left.
The Welsh left-back was on hand to slide and intercept before Gallagher could pounce on the back post.
Two changes at half-time saw the Reds start the second half as the better side, and they didn’t have to wait long before making their way back into the competition.
Three minutes after coming back out, Brown collected a through ball and paused on the ball, with substitute Chaplin running up-field in support.
Brown laid the ball off for Chaplin, who produced a fine low drive towards goal that crept under Walton.
Few would argue against you if you said that Rovers’ second goal on 69 minutes came against the run of play, with Barnsley the much more assured side on the ball for much of the second half.
Mowatt in particular had two chances to put his side ahead, the first on the hour mark a low drive which Walton had to scramble to save on his left, and the second a curling effort from the edge of the box after a one-two with Chaplin, four minutes later.
For Rovers’ second, Rothwell beat Sibbick and cut inside, taking a shot which was blocked and fell kindly for second-half substitute Stewart Downing – who swung his right boot at it from the edge of the box and found the bottom corner.
Ben Williams was then called upon to produce another goal-line clearance in the 75th minute after Danny Graham broke the offside trap on the left and rolled the ball towards goal.
Woodrow then levelled again for the Reds on 82 minutes, squeezing the ball home after Chaplin collected the ball on Walton’s right and played the ball across goal after some good play from Mowatt and Brown to work the ball into the box.
Chaplin had already had another effort from a similar position blocked by the Rovers ‘keeper on 77 minutes, forcing a corner.
Defensive frailty was again to blame as Rovers got the winner, Dack found on the back post after a Downing free kick into the box was headed across goal for the midfielder to net on 86 minutes.
The Reds pushed for another equaliser, with Radlinger even coming up for a late corner, but the home side held on for the three points.
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