Herein, an excellent cathode of ZnO-CeO2/CF was fabricated successfully via one-step electro-deposition method for the degradation of ciprofloxacin (CIP) in sewage by electro-Fenton (EF) technology. The detailed characterizations of ZnO-CeO2/CF material were conducted by SEM, XRD, XPS, CV and EIS. Effects of deposition time, initial pH and voltage value on degradation performance of ZnO-CeO2/CF were investigated systematically. The results showed nearly 100% degradation efficiency was easily obtained at 2 h owing to the large specific surface area of cathode, the good oxygen storage ability and Fenton-like performance of ZnO-CeO2. It was worth to mention that the favorable capability still existed in cathode body after 10 consecutive runs. Moreover, electron paramagnetic resonance (EPR) test and sacrificial agent experiments revealed that the increase of active substance accelerated the degradation efficiency of CIP during the process of valence state transition of Ce3+/Ce4+ or Fe2+/Fe3+.