In the study, CeO2 nanoparticles were successfully decorated on the TiO2 nanotube arrays (CeO2/TiO2 NTAs) photoelectrode by cathodic electrodeposition method in the presence of Ce(NO3)(3) electrolyte. The effect of fabricating parameters including electrolyte concentration, applied voltage, deposition time and calcination temperature on morphology and crystal structure of CeO2/TiO2 NTAs was further investigated. Moreover, the as prepared materials were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM). Meanwhile, the optical and photoelectrochemical (PECH) properties were recorded through ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), transient photocurrent response (i-t) and open circuit potential (OCP), respectively. Furthermore, we evaluated the electrical catalysis (EC), photocatalytic (PC) and photoelectrochemical (PEC) performances of the CeO2/TiO2 NTAs photoelectrode by degradation of methyl orange (MO). Results indicated that the CeO2/TiO2 NTAs exhibited higher EC, PC and PEC activities than that of pristine TiO2 NTAs photoelectrode owing to higher separation of efficiency photo produced electrons-holes (e/h(+)) pairs and visible light absorption.