Elsewhere, Premier League giants and defending champions Manchester United take on Fulham at Old Trafford.
Brighton, who downed fellow top flight opposition Chelsea in impressive fashion have earned a clash with at Carabao Cup finalists Newcastle.
There's a home tie for seven-time champions Aston Villa, who entertain Championship outfit Cardiff City after earning a place in the last 16 with a 2-1 win over rivals Tottenham.
There are two final spots up for grabs, with Crystal Palace facing Doncaster Rovers on Monday night and Nottingham Forest taking on Exeter City on Tuesday.
The winner of the Palace vs Doncaster clash will face Championship side Millwall at home, while the winner of the Exeter vs Forest tie will entertain Ipswich Town.
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Liverpool's quadruple team ended with shock FA Cup defeat to Plymouth
In a tournament that's seen numerous Premier League sides knocked out already, the confirmed sides are only from the top two tiers of English football, but League One Exeter and League Two Doncaster would change that with an upset.
Should they not make it, Plymouth would be the lowest-ranked side left, and they were already by far the story of the fourth round.
The Pilgrims took down a Liverpool side who topped the league phase of the Champions League, are top of the Premier League and through to the Carabao Cup final.
The Devon side started the season in disarray under Wayne Rooney and have conceded 63 goals in the Championship, the highest number of any team in England's top four professional tiers.
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Rooted to the bottom of the table, they now look inspired under new Bosnian coach Miron Muslic who earned the victory thanks to a 53rd minute penalty from Ryan Hardie.
Discussing the new manager post-match, star goalkeeper Conor Hazard told talkSPORT: "He's incredible, from our first meeting, he set the tone really early on, how he wants everyone to be around the place.
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"It's not just about what's on the pitch; it's off the pitch too. He's doing a great job so far.
"You would run through brick walls for him at the moment.
"The way he approaches and speaks to you, especially in front of a group, makes you so hyped and motivated. I don't know how to describe it, but in every way, he could be a motivational speaker of some sort."
Meanwhile, there's an all-Premier League showdown with Bournemouth playing host to Wolves.
And the other tie is an all-Championship affair with Preston North End meeting fellow Lancashire club Burnley at Deepdale.
All fifth round matches will take place around the weekend of March 1/2, with the Wembley final on Saturday May 17.