The former Wimbledon semi-finalist played in the 4-1 win over Switzerland in February but has been replaced in the team for the April 21-22 tie in Stuttgart by 20-year-old Olivia Rogowska, who is ranked 120th in the world.
Rogowska will be making her Fed Cup debut in a tough tie against a Germany team which could feature four top 20 players in Andrea Petkovic, Sabine Lisicki, Angelique Kerber and Julia Goerges.
US Open champion Sam Stosur leads Australia with Rogowska, Jarmila Gajdosova and Casey Dellacqua making up the quartet for the contest, which will be played on clay.
"Sam is one of the best claycourt players in women's tennis at the moment and is capable of leading our team to what would be a memorable victory," captain David Taylor said in a news release.
"It was a difficult decision to choose a team for this tie as we have four girls who are very closely ranked which is a nice problem to have.
"(We) decided to go with Olivia Rogowska, who will be making her debut for Australia, as a reward for her big ranking improvement in the past six months and her performances at the WTA level during the Australian summer."
Australia have won the Fed Cup seven times but their last triumph came in 1974 and they dropped out of the World Group last year after a defeat at the hands of Ukraine.