What's the correct phrase?
She wants to marry a guy with brains.
She wants to marry a guy having brains.
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With brain used to indicate the manner or attitude of the person doing something that shows that he has a good thinking
Having brain means the person own a brain.
She wants to marry a guy having brains is ungrammatical. It should be
She wants to marry a guy that has a brain
Regardless, this sentence doesn't make sense because everyone has a brain.
'With brains' is more like an adjective, describing a trait for an individual, like saying 'a guy with a limp' or 'a guy with a big nose'.
'Having brains' is much less commonly used, and is usually a more general description of someone's behavior, like 'people who have enough brains to drive carefully'.