An electrically-insulative coating for minimizing an electrical conductivity of a metal substrate includes a polymer component formed from a monomer precursor, and a powder component substantially dispersed in the polymer component. The powder component is present in the electrically-insulative coating in an amount of from about 5 parts to about 80 parts by weight based on 100 parts by weight of the electrically-insulative coating. The electrically-insulative coating does not substantially degrade when exposed to from about 100 V to about 330 V at a temperature of from about −50 ° C. to about 500 ° C., and has a dielectric strength of at least about 2,000 VAC/mil. An electrically-insulative coating system and a method of forming an electrically-insulative coating on a metal substrate are also disclosed.