The chalcopyrite CuIn(1-x)GaxSe2 (CIGS) thin films were grown on Mo substrate by electrochemical atomic layer deposition (E-ALD) of superlattice sequencing 2InSe/2GaSe/1CuSe, recently developed on model Au surface by Stickney and coworkers (J. Electrochem. Soc. 161, D141 (2014)). The cyclic voltammetry studies were conducted on copper, selenium, indium and gallium on molybdenum substrate and CIGS films were grown by different numbers of superlattice sequencing. The deposited films were examined for phase and microstructure formations by X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning tunneling microscopy (STM) and energy dispersive spectroscopy (EDS). The XRD pattern corresponded to those of chalcopyrite crystalline phase of CIGS and the crystallite size increased with the number of cycles or periods of whole superlattice sequencing increased. The SEM and STM results were in line with those of XRD by showing that the particle size increased as the number of E-ALD cycles increased. The EDS results revealed the CIGS with near stoichiometry. Finally, the deposited E-ALD films were shown to be photoelectrochemically active with p-type conductivity. (c) The Author(s) 2017. Published by ECS. All rights reserved.