Liverpool, who won the last of their seven League Cups in 2003, will make a midweek trip to Devon to face Paul Tisdale's npower League One outfit at St James Park while Leeds' last meeting with Doncaster ended in a 5-2 win for Simon Grayson's team.
Everton will host Sheffield United, while two of the three Barclays Premier League newcomers were given home ties with Norwich playing MK Dons at Carrow Road and Neil Warnock's QQPR facing Rochdale to Loftus Road.
Fellow top-flight newboys Swansea were handed a trip to Shrewsbury with five-time winners Aston Villa drawn out at home against Hereford.
The unseeded teams were drawn earlier in the day and West Brom and Sunderland both face trips to the south coast to face Bournemouth and Brighton respectively.
Wigan will travel to the winner of the rearranged tie between Crystal Palace and Crawley while Scunthorpe take on Newcastle and Wolves travel to Northampton.
Full Carling Cup Second Round Draw:
Millwall v Morecambe, Blackburn Rovers v Sheffield Wednesday, Bury v Leicester City, West Ham United or Aldershot v Carlisle, Bournemouth v West Bromwich Albion, Crystal Palace or Crawley Town v Wigan Athletic, Peterborough v Middlesbrough, Aston Villa v Hereford, Bristol City or Swindon v Southampton, Exeter v Liverpool, Everton v Sheffield United, Brighton v Sunderland, Shrewsbury v Swansea City, Reading or Charlton v Preston, Norwich City v MK Dons, Northampton v Wolves, Wycombe v Nottingham Forest, Bolton Wanderers v Macclesfield, Burnley v Barnet, Scunthorpe v Newcastle United, Leyton Orient v Watford or Bristol Rovers, Doncaster v Leeds United, Cardiff v Huddersfield, QPR v Rochdale
All ties to be played week commencing August 22.