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Q. How do you know when to use On-reading and Kun-reading?

A. Unfortunately there is no simple way to explain  when to use On-reading or Kun-reading. You need to memorize the pronunciation on an individual basis, one word at a time. However, here are some facts that are worth remembering. 

On-reading is usually used when the kanji is a part of a compound (two or more kanji characters are placed side by site). Kun-reading is used when the kanji is used on its own, either as a complete noun or as adjective stems and verb stems. This is not a hard rule, but at least you can make a better guess. 

Let's take a look at the kanji character for "水 (water)". The On-reading for the character is "sui" and the Kun-reading is "mizu." "水 (mizu)" is a word in its own right, meaning "water". The kanji compound "水曜日(Wednesday)" is read as "suiyoubi." Here are other examples.

Kanji

On-reading Kun-reading
音楽 - ongaku
(music)
音 - oto
sound
星座 - seiza
(constellation)
星 - hoshi
(star)
新聞 - shinbun
(newspaper)
新しい -atara(shii) 
(new)
食欲 - shokuyoku
(appetite)
食べる - ta(beru)
(to eat)

"Kanji Land" lessons include both On-reading and Kun-reading and useful kanji compounds.

Vol. 43: What is On-reading and Kun-reading? 

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