To ejaculate (cum) on a woman's body, other than inside a crevice. Usually on the face or in the eye

External male ejaculation in a pornographic film onto his parnter's body. The term comes from earlier days of pornography in which sex acts were often simulated, and this showed that it was not. It was referred to as the money shot, because customers were willing to pay a higher price for actual than simulated sex.

During the act of sex, either oral, anal or vaginal, when the man pulls out and shoots a load of cum in his partners face.

When fucking a girl in one hole while there's some cash sticking out of another.

This term is often used to describe a pinnacle moment in an event or the best course of action. It doesn't have to be used in a sexual context.

1.Ejaculation over a woman's breasts or face.
2.In a series of pictures, the one with the most sexual content is referred to as the "money shot".

The money shot is derived from the pornographic film industry. When the main actor is unable to ejaculate a second steps in with the sole purpose of ejaculating on the woman (this is why you so often see very little of the man in the final shot, so you can't tell its a different actor.)
Called the money shot because the second actor traditionally gets half the money for doing very little