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As you know, when you drive your car the engine bay is hot. Since hot air can hold more vapour, more precisely the partial pressure of water higher at higher temperature. The hot air in the engine bay accumulates vapour while you drive your car and there is always fresh air going by. But when yo stop your car the air exchange stops, and the initially hot air is trapped in the engine bay. And as the engine bay cools down the extra amount of vapour condenses leaving a small pool of water behind.

It also could be the a/c evaporator drain, the a/c compressor does run with defrost mode

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Q: Why is there a small water puddle under car in engine area during cold weather?
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