Both clubs face all Premier League ties as Wolves face off against Everton at Molineux with Aston Villa travelling to Brentford's Gtech Community Stadium.
Wolves made it into the third round of the competition following a dramatic late win over West Ham United at Molineux on Tuesday evening.
The Old Gold’s first win of the season saw Rodrigo Gomes hit Wolves’ first goal of the new term, before Jorgen Stand Larsen’s brace secured a come from behind victory over their Premier League rivals.
Unai Emery’s men enter the competition at the third-round stage alongside seven other Premier League sides competing in European competitions.
Ironically, Vitor Pereria's men face Everton on Saturday at Molineux in the Premier League while Aston Villa suffered a shock 1-0 defeat at Brentford last weekend.
The fixtures are set to take place during the week commencing 15th or 22nd September.