The tie will take place in the week beginning Monday September 21 at Glanford Park.
The last time the two sides met at Glanford Park was back in October 2006, with the game finishing 0-0. Vale are the lowest ranked team left in the competition.
In the pick of the other games, Liverpool travel to Elland Road to face Leeds and Preston host Tottenham Hotspur.
Draw in full:
Arsenal v West Bromwich Albion; Chelsea v QPR; BoltonWanderers v West Ham United; Barnsley v Burnley; Hull City v Everton; Leeds United v Liverpool; Manchester United v Wolves; Manchester City v Fulham; Sunderland v Birmingham City; Peterborough United v Newcastle United; Carlisle United v Portsmouth; Nottingham Forest v Blackburn; Stoke City v Blackpool; Scunthorpe United v Port Vale; Preston North End v Tottenham Hotspur; Aston Villa v Cardiff City