An ex-ambassador is not ambassador anybody. However, these days, no one pays attention to such niceties, which means that everybody pretty much gets called whatever. Just ask them.

Conversationally, i agree that ex-wife seems much more common that former wife. In writing, though, the use of former doesn't seem so rare. Here's an interesting ngram.

Scarred by the Past, an Ex-Gang Member Aims for Revival - The New York

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