The Olympic swimming campaign started in disastrous fashion when world record-holder Biedermann failed to reach the 400m freestyle final and the women's relay was team eliminated.
Biedermann, who set the 400m free world record of 3min 40.07sec in 2009, at the height of the high-tech suit era, mustered just the 12th-fastest time in the heats led by China's Sun Yang.
"I'm obviously disappointed and now need some time to collect myself," he said after swimming 3:48.50. "It was not so good. I wanted to lead from the front, which had worked well, but I just could not hold back on to it.”
“I didn't go off too fast. It was as it should have been," added Biedermann, who will try to regroup for the 200m free that starts on Sunday.
Germany's women also missed out on a spot in the women's 4x100m freestyle final with the ninth fastest time.
Britain, buoyed by the rapturous support of the home crowd, finished equal fourth in their heat with Sweden, the two countries claiming the last two spots.
The German quartet including 100m freestyle world record-holder and Biedermann’s girlfriend Britta Steffen, along with Silke Lippok, Lisa Vitting and Daniela Schreiber, were fourth in the second heat.
"We may have underestimated the competition," said Steffen, the reigning Olympic 50 and 100m freestyle champion. "With the World Cup bronze medal from last year, we really thought that we were sure for the final. We screwed up, we're mature athletes. Things can't be worse."
Schreiber said the Germans had been too conservative, under advice from their coaches.
"We wanted to keep a little bit in reserve, but apparently that was too much," said Schreiber.