CuIn1-xGaxSe2 (CIGS) semiconductors are promising candidates for thin-film photovoltaics and photoelectrochemical applications. In this work, CIGS absorbers prepared from an industrially benign low-cost pulse electrodeposition technique are used for solar energy harvesting through photovoltaic and photoelectrochemical means. Initially, the cyclic voltammo-gram (CV) of Cu-In-Ga-Se is systematically investigated to understand the reduction potentials. The inferences from the CV are suitably utilized to perform the pulse electrodeposition of CIGS with a two-electrode system. The precursor layers are heat-treated with and without the presence of elemental selenium to form CIGS absorbers. The annealing process (without Se) has yielded films containing agglomerated particles with the desired copper-poor composition and chalcopyrite single-phase CIGS with a demonstrated photoactivity in the liquid junction. The selenized CIGS possesses compact grains with similar composition and has yielded a photoconversion efficiency of 3.9%. The study, with the utilization of an ecofriendly electrodeposition approach and demonstration of CIGS absorbers' efficacy for photovoltaic and photoelectrochemical performance, paves the way for an economic means of solar energy harvesting.