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I went to Merrian-Webster to check on this and found that, just like I've heard many times, there are two pronunciations for "poor":

\ ˈpu̇r , ˈpȯr \

Is there some sort of rule that says which to use in different cases? TIA.

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In most of the US, we say /ˈpȯr/. In New England states, some people say /pu̇r/.

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anonymousIs there some sort of rule that says which to use in different cases?

It's not a matter of "different cases". Once you decide how you want to pronounce it, use that same pronunciation in all cases.

It's a matter of regional pronunciations. In my (very strong) opinion there is only one way to pronounce "poor", and that's \ ˈpu̇r \ (IPA /puɚ/ or reduced to /pʊɚ/). This is the pronunciation in "General American English". Only the West Midland and the Southern accents use the alternative \ˈpȯr \ (IPA /pɔɚ/).

Here's an interesting website with a map by hobbyist Aschmann.

https://aschmann.net/AmEng/

CJ