Chelsea made it to last season's semi-finals before being eliminated 2-1 on aggregate by Arsenal, who itself was defeated by Manchester City in the final.
The two sides last met each other in the Carabao Cup in January 2015 – Chelsea emerging 2-1 aggregate victor on its way to lifting the trophy.
Third round fixtures are due to take place on the week commencing 24 September, meaning Chelsea's trip to Liverpool will come just a few days prior to their Stamford Bridge meeting in the Premier League on the 29th.
One of the other standout ties sees Derby County travelling to Manchester United, as Lampard – who enjoyed great success as a player at Chelsea under Mourinho – prepares to face the Portuguese coach for the first time.
Reigning champion City travels to League One side Oxford United at the start of its defence, while the team it defeated at Wembley in February – Arsenal – will host Brentford.
There are three other all-Premier League ties, with Wolves welcoming Leicester City, Everton hosting Southampton and Watford heading to Tottenham, which has applied for special dispensation to play at a neutral stadium due to the unavailability of Wembley and its new ground.
EFL Cup third round draw in full:
West Brom v Crystal Palace
Arsenal v Brentford
Burton Albion v Burnley
Wycombe Wanderers v Norwich City
Oxford United v Manchester City
West Ham v Macclesfield
Millwall v Fulham
Liverpool v Chelsea
Bournemouth v Blackburn Rovers
Preston North End v Middlesbrough
Wolves v Leicester City
Tottenham v Watford
Blackpool v QPR
Everton v Southampton
Manchester United v Derby County
Nottingham Forest v Stoke City