There are azeotropes - mixtures that distill together at a different temperature than either alone.

You can’t distill ethanol to higher than 95% because of the 95-5 ethanol-water azeotrope that boils at 78.2C, versus ethanol alone at 78.4C.

Methanol-water and methanol-ethanol don’t form an azeotrope so if properly done you can separate methanol via distillation.