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When expressing a superlative meaning ("the most ..."), what is the difference between the usage of もっとも and 一番? (e.g. もっとも大きい vs. 一番大きい)

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Simply, 一番 is colloquial/casual, and 最も is formal/technical. Oh, this is one of the rare cases where 漢語 words are more informal than the 和語 versions.

In addition, 最も can only function as a modifier, while 一番 can work as a noun which means number one.

  • 私が一番だ。: OK
  • 私が最もだ。: NG
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When expressing superlative, both もっとも and 一番 have the same meaning.

Here are the definitions of もっとも and 一番 according to デジタル大辞泉.

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