Arsenal and Liverpool both face difficult fixtures in their first outings in this season's tournament, while there are also all-top-flight games and a host of evenly-matched ties which catch the eye.
It has been a while since Liverpool lifted silverware, however, the trend for fielding second-string sides in the Carling Cup is unlikely to change when the Reds renew rivalries with Simon Grayson's Leeds, who are former Premier League giants, live on Sky Sports 2 & HD2 at Elland Road.
Arsene Wenger's Arsenal are desperate for a trophy and would welcome the League Cup to their collection, but that is unlikely to stop the Frenchman gambling with wholesale changes to his team for the arrival of Championship leaders West Brom.
Top-flight sides Bolton and West Ham, who defeated London foes Millwall in a bad-tempered second-round meeting, clash at the Reebok Stadium, while Sunderland and Birmingham cross swords at the Stadium of Light.
Burnley reached the semi-final of the competition last season and caused a number of shocks along the way, but Owen Coyle's side now hold Premier League status and will want to avoid a shock away at Barnsley.
Blackburn face a difficult trip to the City Ground to take on Nottingham Forest, while Stoke will also have their work cut out when Championship side Blackpool visit the Britannia Stadium.
Portsmouth have endured a wretched start to the season and have yet to record a league win, so under-pressure boss Paul Hart will be nervous when travelling to League One outfit Carlisle.
Championship rivals Peterborough and Newcastle meet at London Road, while Scunthorpe host League Two outfit Port Vale.