QPR, following their relegation from the Premier League, will travel to Exeter City, while Bournemouth and Portsmouth face the prospect of a south-coast derby.
Matches will be played in the week commencing 5 August, with the winners joining the majority of Premier League teams in round two, as well as Reading.
Wigan will enter the competition in round three, along with Swansea and the other Premiership teams competing in Europe.
In further first round action, last season's finalists Bradford will visit West Yorkshire rivals Huddersfield. South Yorkshire meanwhile, will see Rotheram take on Sheffield Wednesday.
Conference Premier champions Mansfield face a trip to Tranmere, while Preston boss Simon Grayson will return to former side Blackpool.
Wolves, following back-to-back relegations, travel to Morecambe, and Leicester, three-time winners of the League Cup, go to Wycombe.
Draw in full:
Bury v Crewe Alexandra
Shrewsbury Town v Bolton Wanderers
Middlesbrough v Accrington Stanley
Doncaster Rovers v Rochdale
Preston North End v Blackpool
Barnsley v Scunthorpe United
Tranmere Rovers v Mansfield Town
York City v Burnley
Notts County v Fleetwood Town
Sheffield United v Burton Albion
Oldham Athletic v Derby County
Carlisle United v Blackburn Rovers
Morecambe v Wolverhampton Wanderers
Nottingham Forest v Hartlepool United
Leeds United v Chesterfield
Huddersfield Town v Bradford City
Rotherham United v Sheffield Wednesday
Port Vale v Walsall
Gillingham v Bristol City
AFC Bournemouth v Portsmouth
Wycombe Wanderers v Leicester City
Brentford v Dagenham and Redbridge
Exeter City v Queens Park Rangers
Charlton Athletic v Oxford United
Southend United v Yeovil Town
Millwall v AFC Wimbledon
Swindon Town v Torquay United
Birmingham City v Plymouth Argyle
Stevenage v Ipswich Town
Cheltenham Town v Crawley Town
Bristol Rovers v Watford
Northampton Town v Milton Keynes Dons
Leyton Orient v Coventry City
Colchester United v Peterborough United
Brighton and Hove Albion v Newport County
Source: DSG
Source: DSG