My personal "shocking" stories don't involve mains power because, well, ..., because I'm a coward when it comes to electricity. Instead, my personal incidents usually involve things like the 15 kV output from a voltage multiplier (yes, it knocked me straight to the floor and it didn't even say "excuse me"), or the 8 kV_pp @1 MHz output developed by a series resonant circuit (yes, the Q-risen voltages are real, even if they are represented by an imaginary number).

The worst shock I've ever seen was at the Superconducting Super Collider Laboratories, when we were commissioning the RFQ (Radio Frequency Quadrupole). It accelerated our charged particle beam to 2.5 MeV. One day the beam dump ground wire came loose. One of the technicians went to reconnect it without thinking about the fact that a 2.5 MeV charged particle stream would have charged it up to 2.5 MV. It literally threw him across the room. He woke up in the hospital, the good news being that he woke up at all.