CuInSe2 thin films with the chalcopyrite structure were electrodeposited on titanium substrates from an acidic sulphate solution containing citrate ions as a complexing agent. These layers were characterized by X-ray diffraction, SEM, X-ray energy dispersive analysis and spectrophotometry of reflected light. The best deposits were obtained atE=−0.97V vs SSE, in a solution adjusted to pH 3.3. The deposition of the binary alloys was also investigated. It was shown that the formation of smooth layers of crystalline definite compounds is correlated with a slow surface process which induces a plateau on the polarization curves.