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If "rarity" is the sole criteria for value, I would imagine a CTO stamp that was postally used could be worth quite a lot to collectors of covers.
As GeoffHa wrote, than it would not be CTO.
CTO is a cancelled unused stamp, thus making it invalid for postal use.
The only way it can have been postally used is as an adornment of the mail item. That would put it in the same category as a sticker of a cat stuck on the item of mail.