Sky Bet Championship new boys Burton will host Premier League Liverpool in the EFL Cup second round.
Jurgen Klopp's side had to play away from home due to Anfield's redevelopment, and were paired with the team managed by former Reds forward Nigel Clough.
Liverpool are the most successful team in the history of the League Cup, winning the competition eight times - most recently in 2012.
Premier League outfit Burnley will make the short trip to League Two Accrington for an enthralling local derby clash, while Shrewsbury will travel to Sunderland and Yeovil to Everton.
Crystal Palace will host Blackpool, while Watford will take on Gillingham at Vicarage Road.
Chelsea must wait until Thursday night to discover their second round opponents meanwhile, with seedings complicating the draw.
Antonio Conte's men will face either Bristol Rovers or Bristol City, with Thursday's first round ties deciding who travels to Stamford Bridge.
If Cardiff beat Bristol Rovers then the Ashton Gate club will head to Chelsea - but if Rovers win they will take on the Premier League club.
The overly-complicated seeding system led to lengthy explanations on both the televised cup draw and on social media - but still handed the 2015 winners a wait to find out their eventual opponents.
Scunthorpe will host either Cardiff or Bristol City in the other half of the protracted draw.
Swansea, who won the cup in 2013, travel to Peterborough, Bournemouth make the trip to Morecambe and Exeter are at home to Hull.
West Brom make the relatively short trip across the Midlands to Northampton, Stevenage are at home to Stoke and Championship big guns Newcastle host Cheltenham.
Leeds travel to Luton, with QPR hosting Rochdale, Blackburn taking on Crewe, Preston facing Oldham, Oxford tackling Brighton, and Reading up against MK Dons.
Middlesbrough travel to Fulham with Derby hosting Carlisle, Cambridge travelling to Wolves and Norwich taking on Coventry in the other ties to be played in the week commencing August 22.
EFL Cup second-round draw
QPR v Rochdale
Scunthorpe v Cardiff/Bristol City
Watford v Gillingham
Peterborough v Swansea
Everton v Yeovil
Millwall v Nottm Forest
Sunderland v Shrewsbury
Luton v Leeds
Chelsea v Bristol Rovers/Bristol City
Burton v Liverpool
Blackburn v Crewe
Accrington v Burnley
Crystal Palace v Blackpool
Morecambe v Bournemouth
Preston v Oldham
Oxford v Brighton
Reading v MK Dons
Fulham v Middlesbrough
Newcastle v Cheltenham
Exeter v Hull
Derby v Carlisle
Northampton v West Brom
Wolves v Cambridge
Stevenage v Stoke
Norwich v Coventry
Ties to be played week commencing August 22.