Holders Wigan Athletic, who scored a major upset when they were relegated and beat Manchester City in last year's final, will travel to Cardiff City, who were promoted to the Premier League at the end of last season.
Everton, whose manager Roberto Martinez left Wigan after taking them to FA Cup glory against City, will face his old club Swansea City in one of four all-Premier League ties.
The other match between top-flight sides pits Capital One Cup finalists Sunderland against Southampton at the Stadium of Light.
Sheffield Wednesday will meet Charlton Athletic in an all-Championship tie and Premier League Hull City travel to Brighton of the Championship.
The winners of the replay between Sheffield United and Fulham will face Nottingham Forest or Preston North End who are also involved in a fourth-round replay.
The standout games are those between City and Chelsea - who met in the semi-final at Wembley last season when City won 2-1 - and Arsenal and Liverpool.
Chelsea, who have won the Cup four times in the last seven seasons, and City, who lifted the trophy in 2011, have met once since the semi-final with Chelsea winning 2-1 in the league at Stamford Bridge in October.
Chelsea coach Jose Mourinho said he was looking forward to the tie.
"If you want to be the best you have to play the best," he told ITV.
League leaders Arsenal, chasing their first silverware since winning the FA Cup in 2005, are unbeaten against Liverpool in their last four meetings and notched up a 2-0 home win over the Merseyside club in November.
The matches will be played on the weekend of February15/16.
Manchester City v Chelsea
Sheffield United or Fulham v Nottingham Forest or Preston North End
Arsenal v Liverpool
Brighton & Hove Albion v Hull City
Cardiff City v Wigan Athletic
Sheffield Wednesday v Charlton Athletic
Sunderland v Southampton
Everton v Swansea City
(Reporting by Mike Collett, editing by Ed Osmond)
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