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We've learnt that お is used for 訓読み and ご is used for 音読み. I want to know why we use お上手 and お電話. Why can't we use ごじょうず and ごでんわ?

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My sense from my class was that the basic rule is as you describe お for 訓読み words and ご for 音読み words but that words which are used with frequency can wind up using お even though what follows is an 音読み. I am merely speculating when I say that the reason is that these words have become naturalized into the consciousness of Japanese people as Japanese words rather than as loan words from Chinese. In the case of 電話 also note that despite the 音読み this is not a Chinese loan word. – virmaior Mar 7 '14 at 8:33
Possibly related: japanese.stackexchange.com/questions/4417/… – 無色受想行識 Mar 9 '14 at 11:01

The general rule is that if the word is of Chinese origin (e.g. uses [音読]{おんよ}み), it uses ご:

  • ご[家族]{かぞく}
  • ご[飯]{はん}
  • ご[本]{ほん} (as in a book, not the counter)

If it is a native Japanese word, it uses お:

  • お[盆]{ぼん}
  • お[手洗い]{てあらい}

Katakana words officially are not supposed to use the prefix at all, however when it is applied it's customary to use お:

  • おビール
  • おトイレ
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