The draw was made on Wednesday night, with PNE and the Reds the last tie out of the hat.
Frankie McAvoy's men reached the last 16 thanks to a 4-1 win over Cheltenham Town on Tuesday, with Liverpool beating Norwich City 3-0.
It is sure to be a sell-out crowd at Deepdale and there is a strong chance it will be chosen for live coverage by Sky Sports too which would swell the coffers further.
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The game is scheduled to take place in the week beginning October 25.
It will be the first meeting between the clubs since they played in the FA Cup at Deepdale in January 2009, Liverpool winning 2-0.
North End and Liverpool have never met in the League Cup in any of its guises.
Fourth round draw:
Chelsea v Southampton
Arsenal v Leeds United
Stoke City v Brentford
West Ham United v Manchester City
Leicester City v Brighton
Burnley v Tottenham
Queens Park Rangers v Sunderland
PNE v Liverpool
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