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I know this is one of the oldest Pokemon version. In ruins of alphs, is there any rare Pokemon there?

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If you mean the actual cave itself, Unown are the only Pokemon that can be caught there.
If you mean outside, Natu, Smeargle, Wooper, Quagsire, Poliwag, Poliwhirl, and Magikarp are the only Pokemon outside.

Aside from being the only place to find wild Unown, there are really no really rare Pokemon.

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ahh thank u :)
Actually, Smeargle is pretty rare (10% chance of finding it) and it's only available in the Ruins of Alph.

Source: http://www.psypokes.com/gsc/walkthrough.php?part=12
I found one in another place -3-
Huh. You did? Where else did you find a smeargle?