In typical conditions, an electrical arc forms when the electric field strength exceeds the dielectric strength of the medium (like air). In a vacuum, there is no medium to ionize, which theoretically makes it difficult for an arc to form. However, electricity can still arc in a vacuum under certain conditions, such as when high voltages are involved or when the electrodes are extremely close together.
I was thinking neon lights. I mean that's basically an arc, just spread out. I think I heard that there's a glow in vacuum too, just not as nice as with neon.