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"What is he?" means that "what does he do for a living?"?
It depends upon the context of the conversation, but yes, sometimes "what is he?" can sometimes be used to ask what he does for a living. For example, you're at a party, pointing out people in a crowd to a companion. "The tall guy is Fred, he's a dentist. That blonde lady is Sheila, she's a teacher. And the real skinny guy is Larry."
"What is he?"
"Larry? He's a chef."
A question about asking one's job.. 
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