Abstract: A method for electroless deposition of Cu.sub.x In.sub.y Ga.sub.z Se.sub.n (x=0-2, y=0-2, z=0-2, n=0-3) precursor films and powders onto a metallic substrate comprising:preparing an aqueous bath solution of compounds selected from the group consisting of:I) a copper compound, a selenium compound, an indium compound and gallium compound; II) a copper compound, a selenium compound and an indium compound; III) a selenium compound, and indium compound and a gallium compound; IV) a selenium compound and a indium compound; and V) a copper compound and selenium compound; each compound being present in sufficient quantity to react with each other to produce Cu.sub.x In.sub.y Ga.sub.z Se.sub.n (x=0-2, y=0-2, z=0-2, n=0-3);adjusting the pH of the aqueous bath solution to an acidic value by the addition of a dilute acid; andinitiating an electroless reaction with an oxidizing counterelectrode for a sufficient time to cause a deposit of Cu.sub.x In.sub.y Ga.sub.z Se.sub.