Binding of heparin with a cationic surfactant such as cetyldimethyl benzylammonium chloride (CDBAC), tetradecyldimethyl benzylammonium chloride (Zeph), cetylpyridinium bromide (CPB), tetradecane pyridinium bromide (TPB) and cetyltrimethylammonium bromide (CTAB) in a near-neutral medium can result in a significant enhancement of resonance Rayleigh scattering (RRS) intensities. The results showed that the reaction conditions and RRS spectral characteristics of these reactions are similar, but their sensitivities are obviously different. Among them, the sensitivity of CDBAC with an aryl and large molecular weight is the highest, while that of CTAB without aryl and with small molecular weight is the lowest. The detection limit for heparin of the former is 11 ng ml(-1) while that of the latter is 33 ng ml(-1). The method has better selectivity and was applied to the determination of trace amounts of heparin in sodium heparin injection samples with satisfactory results. Furthermore, it is discovered that the RRS intensity is related to the structure and molecular weight of the cationic surfactant.