A process for the electrostatic liquid spray application of coatings to a substrate is disclosed. The process comprises forming a liquid mixture in a closed system comprising at least one polymeric component capable of forming a coating on the substrate and a solvent component consisting essentially of supercritical carbon dioxide in at least an amount which when added to the polymeric component is sufficient to render the viscosity of the mixture to a point suitable for spray application. The liquid mixture is then sprayed onto a substrate to form a liquid coating by passing the mixture under pressure through an orifice into the environment of the substrate to form a liquid spray, while negatively electrically charging the liquid mixture by a high electrical voltage relative to the substrate and electric current by electrical discharge from at least one external electrode located near the orifice and close to the spray.