ANSWERS: 2
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For most people, they have to learn how to do it. You learn that (usually) thirds sound more harmonious than, for example, sixths. If you sing in a multi-voiced chorus or choir, the practice makes you more used to being able to make up "your part" in a potential harmonic chord. I have rarely met a person who can do well at singing harmony who has had no music theory or practice in singing in harmony.
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My friends can harmonize almost whenever they want to and they do it effortlessly and without music. I can harmonize individual notes, like the last note at the end of a song, but it takes work for me to be able to harmonize for a whole phrase. I find it much easier when I have at least sheet music in front of me to help me.
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