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Some (not all) of my favourites off the top of my head include:
Luxray started in Gen 4's NU and has been untiered ever since.
Vikavolt's started in Gen 7's NU and dropped to untiered in Gen 8.
Primarina's sitting in UU which isn't awful I suppose.
Banette's gone from Gen 3's RU to 4's NU to untiered.
Mawile's been in Gen 3 and 4's NUs, then dropped to untiered if we don't count its mega. That's in Ubers and OU though. Different story.
Apparently they just love sitting in NU for a sec before dropping off. Kinda sad, but kinda funny it's a consistent trend.
Zekrom's always been in this spot where it's been in Ubers ever since its release, but has usually been a bit of a niche pick in said tier. Which probably mostly has to do with its meh Speed stat and Dragon/Electric both having a type that is immune to them.
Celebi started off very strong in GSC but kept on declining, though I stuck around in OU/UU for quite a while. Phione is not good and even PU doesn't want it. Even Azumarill and Jirachi are kind of on a decline recently...
Mah boi Swampert gladly is on OU, Blaziken in in Ubers, Walrein idk, I have too much Pokémon that I love to list here. Most important tho that mah boi is in OU! I'm so proud of mah boi!