Carling Cup holders Birmingham begin the defence of their crown on Wednesday, while Liverpool and Chelsea enter the fray.
Elsewhere, there is an all-Premier League affair at Goodison Park, Cardiff clash with Championship rivals and Southampton seek to maintain their early-season momentum.
Birmingham suffered relegation out of the Premier League last season, but they were able to get their hands on major silverware as they saw off Arsenal at Wembley.
They will be looking to repeat those heroics this term under Chris Hughton, but they face a daunting third round trip to free-spending Manchester City.
Liverpool are expected to welcome talismanic skipper Steven Gerrard back into their starting XI when they go to Championship high-flyers Brighton, who will have their sights set on a prized scalp.
Chelsea square up to west London rivals Fulham at Stamford Bridge, with Blues boss Andre Villas-Boas hoping he can draw another comparison with compatriot Jose Mourinho and land League Cup glory in his first season in England.
Everton will be hoping that West Brom's Premier League troubles leave them vulnerable, with the Baggies set to arrive on Merseyside in the knowledge that they currently prop up the top flight table.
Southampton sit one place below Roy Hodgson's men on the Football League ladder, with a flying start to the 2011/12 campaign leaving them top of the Championship and firing on all cylinders ahead of a midweek date with third tier outfit Preston.
Promotion is the priority for Cardiff and Leicester this season, but a cup run would not go amiss and both sides will have their sights firmly locked on round four when they go head-to-head.