Astronaut
The first civilian in space was Valentina Tereshkova aboard Vostok 6 (she also became the first woman in space on that mission).
Tereshkova was only honorarily inducted into the USSR's Air Force, which did not accept female pilots at that time. A month later, Joseph Albert Walker became the first American civilian in space when his X-15 Flight 90 crossed the line, qualifying him by the international definition of spaceflight. Walker had joined the US Army Air Force but was not a member during his flight. 
The first people in space who had never been a member of any country's armed forces were both Konstantin Feoktistov and Boris Yegorov aboard Voskhod 1.
European Astronaut Corps
All of the current members of the corps have flown to space, except Maurer. All flown members except Jean-François Clervoy have visited the ISS. German astronaut Alexander Gerst is the member of the corps who has accumulated the most time in space with 362 days 1 hour and 50 minutes. He is the record holder for all the European astronauts in history. The oldest is Hans Schlegel, born in 1951. The corps currently includes one woman, Samantha Cristoforetti, who formerly held the record for the longest spaceflight by a woman. Only two other women have been members of the corps. Marianne Merchez who never flew, and Claudie Haigneré who resigned after two missions to start a political career in France.