The water is heated by the microwaves to a temperature even higher than that of the boiling point. Usually this produces steam, also the cause of the bubbles we see that is characteristic of boiling. But because of certain conditions including the speed that microwaves heat water and the purity of the container and the water itself, the steam doesn't come out. When this happens, the slightest disturbance can cause the pent-up pressure and steam to all rush up simultaneously creating the illusion of exploding water. Of note, though, is that this water is still around or even above the boiling point, so it can cause damage and harm...
Taken from Snopes.com
This type of phenomenon occurs if water is heated in a clean cup. If foreign materials such as instant coffee or sugar are added before heating, the risk is greatly reduced. If superheating has occurred, a slight disturbance or movement such as picking up the cup, or pouring in a spoon full of instant coffee, may result in a violent eruption with the boiling water exploding out of the cup.
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