Rovers made the long journey west to High Valleyfield to take on last season’s Premier League champions.
Darren Wilson opened the scoring before Rovers almost doubled their lead with two minutes of the first half remaining when Smith brought out a fine save from the home ‘keeper with a curling effort from the edge of the box.
It was a missed opportunity that Rovers were soon to regret as they conceded on the stroke of half time.
Valleyfield started the second half with purpose after getting back on terms but the first clear cut opportunity of the half fell to Pittenweem when McCarroll beat the offside trap and raced in on goal two minutes after the restart.
Rovers eventually got their noses back in front on the 67th minute when Lee Allan bundled home a loose ball.
As Valleyfield tried to regroup, Pittenweem went further ahead a minute later when Allan put a great ball through to McGhee, who rounded the keeper to score and make it 1-3.
Rovers completed the scoring in the 73rd minute when Fleming won the ball in midfield and set McCarroll on his way down the left wing. McCarroll’s driven cross picked out Allan who had the simplest of tasks to tap the ball into the net. On Saturday Rovers are on Scottish Amateur Cup duty when they entertain Stirling & District Amateur League side, Tullibody Community AFC.