A novel nanoscale photocatalyst Bi4VO8Cl was prepared by hydrothermal synthesis and characterized. This catalyst was used for the degradation of six pharmaceuticals including metronidazole, acidovir, levofloxacin hydrochloride, sulfonamide, adrenaline hydrochloride, and ribavirin in aqueous solutions by visible light irradiation. It was shown that all the drugs except for metronidazole were mineralized completely during 10 h visible light irradiation, while metronidazole could be degraded easily into biodegradable small molecules. Then metronidazole was selected as a representative drug to evaluate removal efficiency of the photocatalytic system under visible light, ultraviolet light, and solar light, to investigate the degradation kinetics, and to study the possible degradation pathway from degradation products measurements. Results indicated that under the optimal conditions, metronidazole could also be completely degraded within 10 min ultraviolet light irradiation or 6 h solar light irradiation. Therefore, Bi4VO8Cl would be a promising photocatalyst for the removal of pharmaceuticals from waste waters under solar irradiation.