The effect of surfactants on chemiluminescence(CL)reaction of Ce(Ⅳ)-phloroglucinol was investigated.A new chemiluminescent system of Ce(Ⅳ)-phloroglucinol in the presence of tween-40 as sensitizing agent was found.Based on a sensitive chemiluminescence method for the determination of phloroglucinol with flow injection technique was developed.The linear range for phloroglucinol is 5.0×10 -8~5.0×10 -5mol·L -1 with LOD1.0×10 -8mol·L -1.The relative standrad deviation is 2.8% for 5.0×10 -6mol·L -1 phloroglucinol in 11 repeated measurements.The method has been used to determine the content of phloroglucinol in water with satisfactory results.