Ed White was the first American to leave the capsule during the Gemini Program.
Alexei Leonov had done so earlier, and for a while, it looked like the Russians were going to go to the moon before us.
Of course, The USSR had lots of disasters, but they were kept secret till many years later.
The one who burned up upon re-entry is the one I remember. I saw the pics of what was left, it was gruesome, to say the least.
He tossed an alcohol wipe towards a bin, it missed, and landed on an active hot plate. Probably should mention that he was removed sensor adhesive from his chest with the wipe.
I was with my family at the George C. Marshal Space Flight Museum when the PA announced that they had just gotten in raw film of White's space walk. I was one of the first people in the country to see it that day. Dad Worked there as a GE computer programmer contracted to NASA on the Saturn 5 parts inventory. Dad's office was in one of those old Army wooden buildings next to the Headquarters building. He walked out of the door every day and could look up at Dr. Von Braun's penthouse office.