Possibly. Even probably.
On Aug.16, 1960, Joe Kittinger made a jump from 102,800 feet. Of course, Joe Kittinger was in the service, and his jump was not done for personal fame or glory, but for research (Project Excelsior).
(Interestingly, they didn't do that with the Gemini spacecraft, since the launch vehicle--the Titan II--used room-temperature stable propellants. As such, the Gemini capsule relied on ejection seats to "punch out" during the earliest phases of launch.)