CuInSe2 thin films were cathodically electrodeposited on conducting substrates from aqueous solutions containing CuCl, InCl3 and SeO2. Structural characterization were carried out by microprobe, X-ray diffraction and electron microscopy studies. The presence of chalcopyrite phase CuInSe2 was confirmed from X-ray studies. Optical absorption studies indicated band gap values of about 1.1 eV. Electrical characterization was carried out by Hall effect and resistivity studies. The room temperature resistivity and mobility were found to be 2.15×10−3 ω cm and 8.1 cm2 V−1s−1 respectively for p-type films. Diffusion of In into p-type films converted them to n-type. Photovoltaic and photoelectrochemical solar cells were fabricated with Mo/p-CuInSe2/CdS/Au and Mo/n-CuInSe2/I1−I3−/C configurations. The open circuit photovoltage and short circuit current densities were 188 mV and 0.056 mA cm−2 for photovoltaic cells and 172 mV and 2.75 mA cm−2 for photoelectrochemical cells under 100 mW cm−2 intensity of illumination, without optimisation.