An electrical insulator is a material in which electric current does not flow freely. The atoms of the insulator have tightly bound electrons which cannot readily move. Other materials—semiconductors and conductors—conduct electric current more easily. The property that distinguishes an insulator is its resistivity; insulators have higher resistivity than semiconductors or conductors. The most common examples are non-metals.

A perfect insulator does not exist because even the materials used as insulators contain small numbers of mobile charges (charge carriers) which can carry current. In addition, all insulators become electrically conductive when a sufficiently large voltage is applied that the electric field tears electrons away from the atoms. This is known as electrical breakdown, and the voltage at which it occurs is called the breakdown voltage of an insulator. Some materials such as glass, paper and PTFE, which have high resistivity, are very good electrical insulators. A much larger class of materials, even though they may have lower bulk resistivity, are still good enough to prevent significant current from flowing at normally used voltages, and thus are employed as insulation for electrical wiring and cables. Examples include rubber-like polymers and most plastics which can be thermoset or thermoplastic in nature.

Insulators are used in electrical equipment to support and separate electrical conductors without allowing current through themselves. An insulating material used in bulk to wrap electrical cables or other equipment is called insulation. The term insulator is also used more specifically to refer to insulating supports used to attach electric power distribution or transmission lines to utility poles and transmission towers. They support the weight of the suspended wires without allowing the current to flow through the tower to ground.

Electrical insulation is the absence of electrical conduction. Electronic band theory (a branch of physics) explains that electric charge flows when quantum states of matter are available into which electrons can be excited. This allows electrons to gain energy and thereby move through a conductor, such as a metal, if an electric potential difference is applied to the material. If no such states are available, the material is an insulator.

Most insulators have a large band gap. This occurs because the "valence" band containing the highest energy electrons is full, and a large energy gap separates this band from the next band above it. There is always some voltage (called the breakdown voltage) that gives electrons enough energy to be excited into this band. Once this voltage is exceeded, electrical breakdown occurs, and the material ceases being an insulator, passing charge. This is usually accompanied by physical or chemical changes that permanently degrade the material and its insulating properties.

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. 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. When corona discharge occurs, the air in a region around a high-voltage conductor can break down and ionise without a catastrophic increase in current. 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 breakdown or vacuum arc involves charges ejected from the surface of metal electrodes rather than produced by the vacuum itself.

In addition, all insulators become conductors at very high temperatures as the thermal energy of the valence electrons is sufficient to put them in the conduction band.

In certain capacitors, shorts between electrodes formed due to dielectric breakdown can disappear when the applied electric field is reduced.^[relevant?]