Allan Johnston's in-form side secured their place in the last eight with a 3-0 win at Forfar Athletic on Tuesday night and will face off against Ian Murray's side for a place in the last four.
The Buddies, relegated from the Premiership last season, came from behind to see off Annan in their last 16 tie and but have lost their opening two league matches.
Under Jim Jefferies, Dunfermline travelled to Paisley in the second round of the League Cup last season but lost 2-1 after Lewis Spence had given them the lead.
The tie will take place on Saturday 10th October.
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