When subjected to a high enough voltage, insulators suffer from the phenomenon of electrical breakdown and called insulator electrical breakdown.

When the electric field applied across an insulating substance exceeds in any location the threshold breakdown field for that substance, the insulator suddenly becomes a conductor, causing a large increase in current, an electric arc through the substance. Insulator electrical breakdown occurs when the electric field in the material is strong enough to accelerate free charge carriers (electrons and ions, which are always present at low concentrations) to a high enough velocity to knock electrons from atoms when they strike them, ionizing the atoms.

These freed electrons and ions are in turn accelerated and strike other atoms, creating more charge carriers, in a chain reaction. Rapidly the insulator becomes filled with mobile charge carriers, and its resistance drops to a low level. In a solid, the breakdown voltage is proportional to the band gap energy. The air in a region around a high-voltage conductor can break down and ionize without a catastrophic increase in current; this is called "corona discharge". However if the region of air breakdown extends to another conductor at a different voltage it creates a conductive path between them, and a large current flows through the air, creating an electric arc.

Even a vacuum can suffer a sort of breakdown, but in this case the insulator electrical breakdown or vacuum arc involves charges ejected from the surface of metal electrodes rather than produced by the vacuum itself. In case of some insulators, the conduction may take place at a very high temperature as then the energy acquired by the valence electrons is sufficient to take them into conduction band.

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