The world No.1 captured a fourth Australian title in Melbourne last Sunday for a sixth career major before rushing to the airport for a 3am flight back to Europe.
Having spent some brief time at home in Monte Carlo, Djokovic arrived in Belgium on Wednesday and headed straight to the Spiroudome de Charleroi to adjust to the clay courts being used for the tie.
Djokovic will play the second singles on Friday against Olivier Rochus after teammate Victor Troicki faces David Goffin in the opener.
"It's been a long few weeks in Melbourne and exhausting but still very successful," said Djokovic, who missed the entire 2012 Davis Cup season having been instrumental in their maiden 2010 title success.
"Right now I am turning my attention to Davis Cup and I am glad I am part of this team again. I have missed that feeling to be honest and hopefully we can have a successful team."
Meanwhile, the Serbian team have complained about the surface being used.
"It's a very tough situation. We are trying to help the people and the ITF to get the court better. I'm discussing it with them," said Serbian captain Bojan Obradovic.