(especially of a man) good at knowing what to say and how to behave in social situations; appearing relaxed and confident (Oxford)
(especially of a man) confident, comfortable, and polite in social situations (Cambridge)
He was charming and urbane, full of witty conversation. (Oxford)
I looked at the urbane, relaxed figure seated opposite. (Oxford)
charming and urbane
urbane, relaxed figure
Sophisticated
Cultured
Uncivilized
Rude
Urbanely