The phrase is often used in British English to express that someone is being very friendly. When I got lost in London, the police officer was as nice as pie while helping me.
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Non-literal Meaning
Remember, the phrase is not about pies. It's a metaphor for someone's pleasant demeanor. Despite her tough look, she's as nice as pie once you get to know her.
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Informal Setting
Use this expression in casual conversations, not in formal or academic contexts. At the family BBQ, my uncle was as nice as pie to all the guests.