Peroxymonosulfate (PMS) is extensively used as an oxidant to develop the sulfate radical-based advanced oxidation processes in the decontamination of organic pollutants and various PMS activation methods have been explored. Visible-light-assisted PMS activation to construct a Fenton-like process has shown a great potential for pollution control. In our work, BiVO4 nanosheets were prepared using a hydrothermal process and used to activate PMS under visible light. A rapid degradation of ciprofloxacin (CIP) was achieved by dosing PMS (0.96 g/L), BiVO4 (0.32 g/L) under visible light with a reaction rate constant of 77.72-fold higher than that in the BiVO4/visible light process. The electron spin resonance and free radical quenching experiments indicate that reactive species of •O2-, h+, •OH and SO4•- all worked, where h+, •OH and SO4•- were found as the dominant contributors to the CIP degradation. The spectroscopic analyses further demonstrate that the photoinduced electrons were directly involved in the PMS activation process. The generated •O2- was partially utilized to activate PMS and more •OH was produced because of the chain reactions between SO4•- and H2O/OH-. In this process, PMS acted as an electron acceptor to transfer the photo-induced charges from the conduction band of BiVO4 and PMS was successfully activated to yield the high-powered oxidative species. From the degradation intermediates of CIP detected by a liquid-chromatography-mass spectrometer, the possible degradation pathways were proposed. The substantially decreased toxicity of CIP after the reaction was also observed. This work might provide new insights into the visible-light-assisted PMS activation mechanisms and is useful to construct environmentally-friendly catalytic processes for the efficient degradation of organic pollutants.