Cu(In,Ga)Se2 (CIGS) materials are one of the most promising solar cell technologies owing to their large absorption coefficient and tunable direct bandgap, and they have gained considerable commercial maturity. The study herein puts forward the preparation of nanostructured CIGS films containing branched nanorod architectures, which is reported for the first time. The process employs an economic pulse-reverse electrodeposition technique by utilizing the fundamentals of electro-reduction and oxidation to fabricate nanostructured CIGS and completely avoids conventional energy-intensive high-temperature annealing/selenization step. Comprehensive characterization of nanoarchitectured films reveals the stoichiometric composition and chalcopyrite structure with dominant (112) orientation. Nanostructured CIGS exhibits excellent photoactivity with a photocurrent density of 4.31 mA/cm2 at -0.13 V vs RHE in a liquid junction, which is highest for a bare CIGS film and is attributable to its inherent high interface area and better charge transport properties compared to planar films. The ability to produce such efficient nanostructures using an economic, scalable, sustainable, and eco-friendly approach can considerably reduce fabrication costs compared with existing high-temperature bulk material preparation methods. © 2018 American Chemical Society.