AbstractSorbitan ester surfactants are very complicated mixtures. An improved and simple reversed phase high performance liquid chroma tographic (HPLC) method employing a C18column has been developed for the rapid separation of sorbitan ester surfactants and the quantitative determination of the distribution of sorbitan mono‐, di‐, tri‐, and tetraester fractions. The sorbitan ester distribution of the six Span and Arlacel surfactants studied was calculated using relative response factors obtained from analysis of pure glycerides of fatty acids. The effects of mobile phase composition on the accuracy and reliability of the distribution values calculated for the sorbitan esters were investi