The crash took place in the Barra region of Rio de Janeiro, the German Olympic team (DOSB) said in statement.
"Early today two members of the staff of the German Olympic team were injured when they were involved in a serious car crash," the DOSB said.
"One of them was seriously injured."
"Both are receiving medical treatment in close coordination with our medical team."
The DOSB said it would not be releasing more information on the severity of the injuries for now.
Games organisers confirmed the accident and said the German team mates involved included one of the coaches from the German canoe slalom team.
"One of the coaches from the German canoe slalom team and another member from the German team were victims of a car accident coming back to the village in a cab," Games spokesman Mario Andrada told reporters.
"He was seriously injured," Andrada said, referring to the man he had identified as a coach.
Security and traffic have been a main concern for teams at the Rio Games while several official Olympic buses have been involved in traffic accidents.
Earlier this morning a bus carrying journalists to one of the Olympic venues scraped another bus. No one was hurt in that incident.
(Reporting by Karolos Grohmann, editing by Susanna Twidale)
