Actually... Fire Spin can be quite useful on Ninetales for example. Will-o-Wisp, Confuse Ray and Fire Spin is a pretty darn annoying combo for the opponent, it only works in competitive battling, though.
Let's see... Hyper Beam for starters, but Water Gun, Rollout and Vine Whip are also overpowered in the show (come on, Water Gun seems to have as much power as Hydro Pump -_-). Ash's Bulbasaur and Chikorita both kicked butt with Vine Whip, but it really sucks in the games.
Needless to say why Rollout is on the list... seriously, I remember the Phanphy from ''Spell of the Unown'' that beat Onix with one hit from Rollout, Ash also haxorizes people with Donphan's/Phanphy's Rollout.
There are much more, too...