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Shiny Poliwag at braille ruins place in sevii islands was my first. As a kid i was bored and exploring the islands, tossed my rod into that little freshwater pond around the tomb thingy, boom Shiny Poliwag, caught that shit.
Second was a Shiny machop at Mt. Ember on that same save file.
Third was ANOTHER Shiny Machop on my Firered replay a few years ago
Fourth was a Shiny Pidgeotto on Gold, because bro and evolved, named her "Shinecock", helped me whomp Red with attract + toxic faggotry
Fifth was a Shiny Gastly i encountered playing a hack called Pokemon Liquid Crystal, early game so i happened to have no balls, ragequit immediately.
Sixth was a shiny Flabebe that popped out on my first playthrough of X, also became a bro and evolved twice.
Most recent was a Shiny Geodude on a Gold romhack called Pokemon Christmas, became bro, evolved into graveller.