In HAc-NaAc buffer medium with pH 3.0-5.0, Chlorpromazine can react with some anionic surfactants (AS) such as sodium dodecylbenzene sulfortate (SDBS) sodium dodecyl sulfate (SDS) and sodium lauryl sulfonate (SLS). As the result, the Resonance Rayleigh scattering (RRS) was enhanced greatly, and a new RRS spectrum appeared. The maximum RRS wavelengths of three anionic surfactants were located at 277, 369 and 277 nm, respectively. The method has a high sensitivity, the detection limits for three anionic surfactants are 0.018 mu g/mL for SDBS, 0.046 mu g/mL for SDS and 0.200 mu g/mL for SLS. There is a linear relationship between the RRS intensity and the drug mass concentration in the range of 0.09-10.0 mu g/mL for SDBS, 0.15-15.0 mu g/mL for SDS and 0.67-12.5 mu g/mL for SLS, respectively. In this work, the spectral characteristics of RRS, the optimum conditions of the reaction and the properties of analytical chemistry were investigated. A sensitive, simple and new method for the determination of anionic surfactants based on RRS was developed.