Do they mean the same thing? What situations should I use one over the other?
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Could you explain where you've run across these terms and why you think they might be equivalent? They're almost opposite in meaning. – mamster Nov 13 '18 at 0:42
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In a manga. It had 黄金郷 and 黄金都市 in similar contexts. – Bryan Tan Nov 13 '18 at 3:54
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1@BryanTan Oh, that's 郷【きょう】, not 郷【ごう】... – naruto Nov 13 '18 at 4:50
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The manga didn't have hiragana, my mistake. – Bryan Tan Nov 14 '18 at 11:31
都市 is a little stiff word that means "city" or "urban area". See: What is the difference between 市, 都市, 都会 and 市街
郷【ごう】 is an uncommon word that roughly means "countryside", "country town", "town", etc. It's also a rare name suffix for small districts in some towns/villages. Practically speaking, you probably don't need this word outside of this common idiom.
EDIT: -郷【きょう】 is a rare suffix that roughly means "village" or "town". You would see it only in a few fixed compounds including 温泉郷.