1. Valentina Allegra De Fontaine and High Evolutionary

2. He Who Remains

3. Death and The 3 other Watchers from What If S3

4. Cassandra

5. Dar-Benn

6. Exiled Kang

7. Gravik

I'm not counting Kingpin nor Thunderbolt Ross yet as I consider them more of Infinity Saga Villains then Multiverse Saga Films.

I'm going with the High Evolutionary.

Also as a side, I don't think that Darkhold Wanda is a Phase 5 Villain unless there was a evil Wanda during Season 2 of What if that I missed.

High Evolutionary

Cassandra Nova and the High Evolutionary. Also Scarlet Witch was a Phase 4 villain. Not a Phase Five villain.

Cassandra Nova