I was working in a lab with a 3kVA AC source powered from 380V 3-phase. It was part of a rack system, and we needed to move it to another room, to hook up to some equipment in our thermal chamber. I had only recently started working there, and was a bit fuzzy from drinking the night before. For some reason I thought I'd turned off the breaker, when I hadn't. So I sat down behind the rack and unscrewed the earth connector, and was about to start unscrewing the live conductors, when my lab partner shouted, "STOP! Don't move!" He ran over and turned off the breaker, and when the enormity of what almost happened hit me I about shat my pants.
Closest call I've had. I'm probably lucky to be alive. Gave me a lot more respect for procedure and checklists.
Hm, haven't actually had any really bad shocks, nothing above ~20V and a few mA, but a guy I was working with once shorted a 400V cap with his screwdriver while working on an off-line SMPS, plugged into mains and turned on. I was looking right at it, and the flash gave me purple spots in my vision for half an hour, and the bang sounded like a .22 rifle. EDIT: No wait, I do remember getting a mains shock once, just briefly while I was unhooking a stereo from behind a TV. I was reaching around behind without a clear view of what I was doing, and I brushed the pins of the mains connector while it was halfway out. Hurt like a sonuva, but no permanent damage.