A process is provided for coating a substrate with a film which includes at least one vaporizable solvent component and at least one solid component using an electrostatic discharge. A coating solution which includes at least one vaporizable solvent component and at least one solid component is introduced into an atomizing zone and atomized to produce drops. The drops so formed are mixed with an air or gas stream to form an aerosol, subjected to an electrostatic discharge, and blown out of the atomizing zone into a vaporizing zone, where a large portion of the solvent component is vaporized so that the individual drop size of the aerosol is about 50 to 90 percent by volume smaller than the volume of the drop size of the aerosol. Subsequently the aerosol is sprayed onto a charged substrate in an application zone, and then dried so as to fuse the solid components and form a film on the surface of the substrate.