The visitors have already been through a round of the competition, thrashing fourth-tier Barrow 6-0 in August, while both sides come in on the back of 3-0 victories in the Premier League.
After his appointment as Chelsea manager in January, Thomas Tuchel guided the Blues to the Champions League title and a fourth-placed finish in the Premier League last season.
They will likely have headed into the new league campaign with the hopes of prevailing in the title race, and they currently occupy the summit of the table with 11 points from their opening five outings.
That comes down to equal efficiency at both ends of the pitch, having only conceded one goal from their five games while just one side have scored more than the 12 goals that Tuchel's men have netted so far.
The Champions League winners come into Wednesday's cup clash on the back of a dominant 3-0 victory over Tottenham Hotspur in Premier League action on Sunday, as Thiago Silva, N'Golo Kante and Antonio Rudiger all got on the scoresheet in the second half.
That win further improved Tuchel's eye-catching record as Chelsea boss, having now won 26 of his 38 games in charge, while only losing five and conceding 23 goals, and he will be keen to push for every possible piece of silverware this season, as they make their first appearance in this year's EFL Cup.
They meet an Aston Villa side who had a mixed start to the new term, and currently sit 10th in the top flight.
After an opening defeat to Watford, Dean Smith's men bounced back with a 2-0 win over Newcastle United, before being held to a draw by Brentford and meeting Wednesday's opponents at Stamford Bridge.
In the recent league meeting between these two sides, Tuchel's men came out with a dominant victory, as Romelu Lukaku hit a brace alongside a Mateo Kovacic goal, but they again bounced back to dish out a 3-0 thrashing of their own last time out.
The Midlands outfit took on Everton on Saturday, and Matty Cash and Leon Bailey found the net quickly either side of a Lucas Digne own goal in a rampant 10-minute spell in the second half to see them leave Goodison Park with newly-found confidence.
They progressed to this stage of the competition with a dominant win over League Two side Barrow, as prospect Cameron Archer hit a hat-trick alongside an Anwar El-Ghazi brace and a Frederic Guilbert goal.
Having been handed a particularly tough draw, Smith's men will look to gain revenge for their Premier League defeat and dump the heavily-fancied Blues out of the competition to strengthen their bid for the trophy.
Chelsea will remain without first-choice goalkeeper Edouard Mendy, who missed out against Tottenham Hotspur on Sunday, while winger Christian Pulisic is also expected to continue a spell on the sidelines.
Tuchel will likely use this opportunity to rotate his squad, with the likes of Timo Werner, Callum Hudson-Odoi and Ben Chilwell expected to feature from the start, while centre-back Trevoh Chalobah will also play a role after making an impressive start to the Premier League campaign with a goal for his boyhood club.
Spanish midfielder Saul Niguez should start, having made his Blues debut in the victory over Aston Villa following his loan move from Atletico Madrid.
Aston Villa have a far longer list of issues to deal with, as Matty Cash, Matt Targett and Leon Bailey all pulled up with muscle injuries in the win over Everton, while John McGinn was replaced as a concussion precaution, with all four expected to sit out alongside Trezeguet and Keinan Davis.
Despite the young squad impressing against Barrow, Smith will likely add more experience as they face far tougher opposition, with the likes of Bertrand Traore and Ollie Watkins expected to play key roles.
The game offers a good opportunity for minutes for French midfielder Morgan Sanson, who is yet to hit the ground running at Villa Park after making the switch from Marseille in January.
Chelsea possible starting lineup:
Arrizabalaga; Christensen, Chalobah, Azpilicueta; James, Niguez, Kovacic, Chilwell; Hudson-Odoi, Werner, Ziyech
Aston Villa possible starting lineup:
Steer; Konsa, Tuanzebe, Hause, Young; Nakamba, Sanson; Traore, Buendia, El Ghazi; Watkins
We say: Chelsea 2-0 Aston Villa
Tuchel has developed a well-oiled machine at Stamford Bridge, and they will certainly not want to see their momentum slowed with a cup defeat.
Even if they rest several key players, the Blues still boast more than enough quality to come out of Wednesday's clash unscathed and progress to the next round.
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