From Damn Interesting:
In the absence of atmospheric pressure water will spontaneously convert into vapor, which would cause the moisture in a victim’s mouth and eyes to quickly boil away. The same effect would cause water in the muscles and soft tissues of the body to evaporate, prompting some parts of the body to swell to twice their usual size after a few moments. This bloating may result in some superficial bruising due to broken capillaries, but it would not be sufficient to break the skin.
Within seconds the reduced pressure would cause the nitrogen which is dissolved in the blood to form gaseous bubbles, a painful condition known to divers as “the bends.” Direct exposure to the sun’s ultraviolet radiation would also cause a severe sunburn to any unprotected skin. Heat does not transfer out of the body very rapidly in the absence of a medium such as air or water, so freezing to death is not an immediate risk in outer space despite the extreme cold.