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I'm extremely confused about whether there are any rules to use On-reading or Kun-reading for kanji words.

A good example is 「弱者」vs「若者」. The former one is On-reading 「じゃくしゃ」, while the latter one is Kun-reading 「わかもの」. However I can't notice any significant differences just from the kanjis. Without checking dictionary, I might guess 「若者」 is also pronounced as 「じゃくしゃ」, similar as 「若年」（「じゃくねん」）

billzt
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Sometimes kanji compounds use kun-yomi readings for both characters (instead of the 'expected' use of on-yomi). This is just a feature of kanji that learners have to come to terms with. The general guidelines for reading kanji contain many exceptions.

This has been discussed at length on the site already. See below:

kandyman
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  • Well, according to https://japanese.stackexchange.com/questions/43197/general-guidelines-for-choosing-訓読み-vs-音読み-in-kanji-reading, does it mean that 「若者」is just one of kun'yomi compounds that have only been memorized without any guidelines? – billzt Sep 05 '20 at 09:10
  • Yes. Answered edited. – kandyman Sep 05 '20 at 09:15
  • @billzt Just to be clear, we aren't talking about a handful of exceptions where you can just memorise the list. We're talking about a lot of exceptions. – user3856370 Sep 05 '20 at 09:17
  • The guidelines generally hold, but yes, there are a lot of exceptions. – kandyman Sep 05 '20 at 09:20
  • @billzt But it should also be noted that it's not purely rote memorization (even though it is at the beginning), because with experience you can come to develop a feel for which way words should be read. – By137 Sep 05 '20 at 10:24