Chelsea travel to Swindon and Sunderland begin life without Paolo Di Canio on a packed night of Capital One Cup action.
The clubs competing in Europe begin their domestic cup campaigns on Tuesday night and there is a repeat of the FA Cup final as Manchester City face Wigan Athletic, while Tottenham Hotspur visit Aston Villa.
Chelsea last won the League Cup in 2007, during Jose Mourinho's first spell at the club, and were beaten by eventual champions Swansea City in last season's semi-finals. There have been questions asked of Mourinho's tactics and selections in recent weeks and he is set to make wholesale changes for the clash with Swindon Town, although that should mean Juan Mata gets an opportunity to show his worth.
The only match Sunderland have won so far this season came against Milton Keynes Dons in the second round, and Di Canio paid the price for their poor form as a reported player revolt led to him being sacked after Saturday's 3-0 defeat by West Bromwich Albion. A number of names have been linked with the vacant role but it is Kevin Ball who will take temporary charge against Peterborough, who are flying high in League One and thrashed Reading 6-0 in the previous round.
There have been managerial changes at Manchester City and Wigan since the Latics' shock FA Cup final victory in May, and the teams that take to the field at the Etihad Stadium will also look very different as key players are rested. Both sides played, and won, on Sunday, with Manuel Pellegrini's City producing a wonderful performance to demolish derby rivals United 4-1.
Tottenham are another team who will have had little more than 48 hours to recover from their weekend exertions by the time they take on Aston Villa. Paul Lambert's men suffered a shock defeat at the hands of Bradford City in last season's semi-finals.
Everton, the only remaining unbeaten team in the Premier League, journey to Craven Cottage to face top-flight rivals Fulham, who have not won any of their last six matches at home and go into Tuesday's clash on the back of a 2-0 loss to Chelsea.
There is another all-Premier League affair as West Ham United entertain Cardiff City at Upton Park. The sides have already met once this season, with the Hammers prevailing 2-0 on the opening day.
Norwich City registered an emphatic 6-3 victory over Bury in the previous round and now head to Vicarage Road to meet in-form Watford, while Southampton will look to follow up a surprise 1-0 win against Liverpool in the Premier League by negotiating a home tie with Bristol City.
Elsewhere, Hull City host Huddersfield Town at the KC Stadium, Leicester City take on East Midlands rivals Derby County and Burnley lock horns Nottingham Forest in a contest between two sides going well in the Championship.