VOY 3x23 Distant Origin [2] also in-universe establishes convergent evolution is very likely to create humanoids (makes no reference to the other two episodes, as far as I remember, but it's kinda wishy-washy in that it could be highly likely because of the two progenitor species).
That said, there's plenty of non-humanoid aliens. Off the top of my head: Q, the Tholians, the Caretaker's species, the two aliens from TOS 2x01 Catspaw (shown to be tiny and kinda birdlike in the final scenes), and Species 8472.
[0] https://memory-alpha.fandom.com/wiki/Return_to_Tomorrow_(epi...
[1] https://memory-alpha.fandom.com/wiki/The_Chase_(episode)
[2] https://memory-alpha.fandom.com/wiki/Distant_Origin_(episode...
I kid; I know you said "at least".
[0]https://memory-alpha.fandom.com/wiki/Unexpected_(episode)
(Though I admit that the ENT example was certainly unique in the differing biologies)
Sometimes real constraints (eg costuming/budgets/etc) can result in really clever explanations that strengthen the storytelling/worldbuilding.