Suppose a new word is coined in a novel/manga/video game etc, which is
composed of two kanjis, with no kanas. Which reading should I expect to use,
kunyomi or on'yomi? If it is on'yomi, should I use Go'on, Kan'on or To'on?

Edit: Sorry for the possible confusion, but I mean, in the situation where I
encounter a newly-coined word with no reading attached, how should I know the
correct reading?

In Chinese (of which I am a native speaker), readings of a homograph (多音字,
characters with multiple readings) are distinguished by meanings, so it's easy
to get the correct reading.
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readings onyomi
When a new word is coined, should onyomi or kunyomi be used?
You're free to choose!

If the new word is gonna be a place/person name, then the existing convention
is that you may use any Kanji and attribute any readings to it, for example,
you could use the Kanji 回 and have it read as `BANANA` if you want.

If the terms is not a name, you're still free to choose to assign it the on-
reading, the kun-reading, or even a special reading. If I create a new term,
let's say, 雨流, I can have it read as うる, うりゅう, あまながし, あめながし, or even a special
reading like ゆばし or クール・デ・プルイー or whatever. So long I communicate this with my
audience clearly, there's no problem. In fact, giving newly-coined terms in
pretty common.

Example of special readings of newly-coined terms:

東京{とうきょう} 喰種{グール}  

[青眼の白龍]{ブルーアイズホワイトドラゴン} (Blue eyes white dragon from YuGiOh)

Even in the standard language, there are a TONS a special readings for Kanji
pairs, the most common ones being 今日{きょう}、昨日{きのう}、明日{あした} so this concept of
special reading is not strange to Japanese people at all.
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answer