In this paper, we chemically synthesized interconnected nanoflake-like CdS thin films for photoelec-trochemical solar cell applications and subsequently irradiated them with electron beam irradiation atvarious doses of irradiation. The as-synthesized and irradiated samples were characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high-resolution transmis-sion electron microscopy (HR-TEM), and electrochemical measurements. XRD and XPS results confirmedthe formation of CdS with a hexagonal crystal structure. FE-SEM and HR-TEM studies confirmed the pho-toelectrochemical performance, which was dependent on the surface morphology. The calculated valuesfor efficiency demonstrated an outstanding photoelectrochemical performance with a fill factor of 0.38and efficiency of 3.06% at 30 kGy. The high photoelectrochemical performance may be due to the inter-connected nanoflake-like nanostructure and higher active surface area of the CdS samples. These resultsshow that the electron beam irradiation is capable as an electrode for photoelectrochemical solar cells.