Abstract One-step assembled CdSe/CdS (core/shell) quantum dots (QDs) were deposited onto ZnO nanowires (NWs) and characterized for their structure, morphology and optical analyses. As deposited ZnO NWs array were wurtzite in structure. During a single hydrothermal cycle a layer of ∼4 nm CdSe/CdS QDs was formed onto ZnO NWs and overgrowth evidenced with an additional 2–5 layers due to which, (a) absorbance density, and (b) Raman Shift of 1LO mode (from 286 cm −1 to 296 cm −1 ) increased and (c) the photoluminescence intensity of the near band-edge emission peak at ∼379 nm decreased. Due to more accumulation of CdSe/CdS, photoelectrochemical cells of ZnO-based photoelectrodes designed for 1–4 cycles of CdSe/CdS onto indium-tin-oxide substrate demonstrated increasing power conversion efficiency trend from 0.18% to 1.29% whereas, for 5th cycle power conversion efficiency, due to an increased series resistance, decreased to 1.12% on account of an accumulation of several QDs.