You could actually pee into vacuum, however it would not be pleasant by any means, for males your skin can withstand slightly more than 1 atmosphere of pressure differential down there, however it would result in an almost instant forced erection which would be almost black out painful,
Now you would not freeze, space is an insulator, however all fluids on the surface of the skin and held in your pours would flash boil due to vapour pressure, and your blood pressure would continue swelling in the skin surrounding,
Now as men have more length to drop the pressure across they stand a better chance of resisting forced urination, however when you finally let go, it would pull your bladder to hard vacuum and likely lead to both bladder and kidney bleeding.
From a few home hobbiests pulling there arms down to fractional vacuums, its painful, however they retain muscle movement it is however limited, and leads to both swelling, and depending on the rate of change the feeling of standing up too fast.
As for the actual ISS toilet, it uses a vacuum pump to draw air and the fluid down the hose,