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The first Valentines Vulpix I came across was a shiny Yellow. Then the only two I've missed were Green and Pink, though now I have a Green one. I also came across a shiny Red one and caught it after getting a normal Red one.
And about 10 clicks after finding a normal Blue one, I ran into ANOTHER normal Blue one. /sob
I can only seem to get them on VDex. I'm a sad person that way. /sob.
I've been Pokeballing my Vulpixs rather than Ultra Balling them (well... I pokeball'd Colette... go fig) because I'm greedy and I want shinies so I'm using my Ultra Balls when I see Shiny. Which is why I don't have a Ditto yet.
I use Ultras for Shinies and Legendaries (and perhaps some Retros). Sooo... pretty much for anything that I want to guarantee a catch (or more guarantee a catch, fml).
I should probably carry one for RB retros because sob I haven't managed to catch RB Gastly.
Since you can't do the exact Bug Catching Contest in Johto, you can buy Compé Balls (or whatever they're called) and "simulate" it, where you'd find the same Bug Pokemon (plus roamers) you would in the actual contest rather than the normal Pokemon that show up in National Park.