Copper indium diselenide (CuInSe2) films have been prepared by pulse electrodeposition technique on Molybdenum substrate followed by post-deposition annealing at 550°C. Optimization of pulse parameters by varying the pulse duration (duty cycle) in order to achieve high quality films has been reported. Appropriate manipulation of pulse parameters has resulted in a novel flake-like crystallite morphology and better control over the composition of individual elements. The CIS thin films were comprehensively characterized using SEM-EDS, FIB, XRD and UV-DRS to study their morphology, phase constitution, etc. and PEC (photoelectrochemistry) measurements were also carried out to ascertain the photoelectrochemical performance of the CIS absorber layer. The bandgap of the CIS films was determined to be 1.02 eV. The flake like crystallite morphology observed in CIS thin films under the optimized processing conditions was found to yield enhanced cathodic photoresponse under solar simulated light with a photocurrent density of 20 μA/cm2 (observed at a potential of -0.6 V vs. SCE). The films exhibited a photoresponse typical of a p-type semiconductor. © 2013 The Electrochemical Society.