Many researchers have shifted their interest towards eco‐friendly, cost effective, and environmental‐based metal oxide nanoparticles. Herein, Cu2O nanoparticles are synthesized via green method for water splitting application. The prepared materials are characterized structurally and morphologically by field emission‐scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), X‐ray photoelectron spectroscopy (XPS) Raman, and UV–visible spectroscopy. It is found that size and morphology depend strongly on OLE concentration and reaction time. The temperature increase leads to the formation of copper oxide (CuO) nanoparticles, which exhibit quantum confinement behavior and have an optical band gap that increases with decreasing size. Photoelectrochemical (PEC) tests of the coated graphite with Cu2O nanoparticles show a severe instability of Cu2O under irradiation due to the oxidation state that can easily change. For that, a protective overlayer of cuprous sulfide Cu2S is successfully grown on the top of Cu2O nanostructures to stabilize the photocathode. After Cu2S deposition, the measured photocurrent is significantly improved. Thus, this material is very promising for hydrogen generation by water splitting.