Thin films of and have been electrodeposited at temperatures from 21° to 120°C from propylene glycol solutions of , elemental sulfur, and . The films were grown on a variety of substrates, including indium tin oxide (ITO) and tin oxide (TO) coated glasses, graphite, nickel, tin and titanium. The stoichiometry of those films grown at room temperature can be controlled through the electrolyte stirring rate which controls the rate of sulfur diffusion toward the cathode. Heterojunction‐like double‐layer structures of on and on were electrodeposited by changing the stirring rate midway through a deposition. Those films grown at room temperature had nearly structureless x‐ray diffraction spectra, while those grown at high temperatures were polycrystalline. X‐ray microanalysis data indicated a continuous copper‐sulfur atomic ratio from 2.33 to 1.06. The films were brown to dark‐gray, and the films were blue‐green to black. The apparent absorbance edge minimum shifted continuously from 835 to 575 nm as the sulfur content of the films increased, and the apparent indirect or nondirect bandgaps of the least copper‐deficient but nearly amorphous films electrodeposited at room temperature were in the 1.25–1.50 eV range.