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grammar is interjection

"of all people" is a type of idiom

Definition

Indicates "more than anything else" or "suprisingly". Emphasizes the thing named. Can be applied to various things.

Examples of how the word is used

of all people illustration You of all people should know better.
of all people illustration Politics, of all things, does not exist in a vacuum, but rather like seeds in dirt, grows with a persistent sprinkling of cash, promises of power, etc.