PNE started brightly as Sam Cadwallader turned in a cross from Michaela Barlow on six minutes for the Whites to take a 1-0 lead.
Doncaster hit back and equalised on 17 minutes and took a surprising lead on 24 mins, from a free kick headed in at the far post.
On 44 minutes Fiona Dransfield met a cross from Michaela Barlow for PNE to equalise.
Mel Martin put PNE 3-2 up on 52 minutes, driving a superb pass from Louise Cafferkey into the back of the net.
Despite PNE having most of the play, Doncaster took the initiative equalising on 65 minutes.
PNE came back strongly in the final ten minutes, but couldn't fire home the winner, and the game was cruelly snatched away from them in the last minute, Doncaster grabbing the winner, to secure victory and the three points.
PNEWFC entertain Blackpool Wren Rovers on Sunday in the second round of the WFA Cup at Bamber Bridge FC, kick off 1pm.
Final score: Doncaster Rovers 4
PNE WFC 3
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