Based on their similarity in chemical properties, rare earth elements were able to form stable coordinated compounds with arsenazo Ⅲ which were extractable into butanol in the presence of diphenylguanidine. The butanol was removed under reduced pressure distillation; the residue was dissolved with diluted hydrochloric acid. As was released with the assistance of KMnO4 and determined by hydrogen generation-atomic fluorescence spectrometry in terms of rare earth elements. When cesium sulfate worked as standard solution, extraction conditions, KMnO4 amount, distillation temperature, arsenazo Ⅲ amount, interfering ions, etc were optimized. The accuracy and precision of the method were validated using national standard certified materials, showing a good agreement. Under optimum condition, the linear relationship located in 0.2~25 μg·mL-1 and detection limit was 0.44 μg·mL-1. After the herbal samples were digested with nitric acid and hydrogen peroxide, the rare earth elements were determined by this method, showing satisfactory results with relative standard deviation of 1.3%~2.5%, and recoveries of 94.4%~106.0%. The method showed the merits of convenience and rapidness, simple instrumentation and high accuracy. With the rare earths enriched into organic phase, the separation of analytes from matrix was accomplished, which eliminated the interference. With the residue dissolved by diluted hydrochloric acid after the solvent was removed, aqueous sample introduction eliminated the impact of organic phase on the tubing connected to pneumatic pump.