It is shown that by changing, in the negative direction, the potential of citric aqueous solutions containing Cu(II), In(III) and Se(IV) under cathodic polarization, it is possible to obtain films such as CuSe, Cu3Se2, CuInSe2 and In-enriched CuInSe2. The values of the potentials under which these compounds are formed depends upon the rate of deposition, the speed of ion mass transfer in the solution, the conductivity or the electrolyte, the cathode surface area and the electrolyte temperature.