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When we happen to know the NATO alphabet we will use it in international situations, where the other one is speaking a different language from our own.
But most of the people I know are not that familiar with it and will have to think hard beforehand or need to substitute at least some of the letters.
What I see in the Netherlands, people (still mostly men) who have been in the army use it almost full time, people who work in international situations often know it. The people who have been into radio communication (ham radio and its brothers) will know it. And that is about it.
The rest of us uses first names in the longer form, hoping that the names are spelled with the same initial for the people we talk with.