The 25-year-old defender last featured as a substitute in the Blues' 0-0 draw at Swansea, but ended the game limping and hasn't appeared for Benitez's side since.
The Selecao will face Roy Hodgson's men on Wednesday at Wembley, however the former Benfica defender is awaiting confirmation on the extent of his injury and could miss out on lining up alongside club teammates Oscar and Ramires against the Three Lions.
Luiz told Globoesporte: "I didn't play for three matches because my calf still hurts. Today I'm going through some exams with [Brazil's physician Jose] Runco, he asked me. I'm training at 100% already and I hope to play for Selecao."