Abstract The purpose of this study was to investigate the interfacial properties of sorbitan monoesters (Span 20, 40, 60, and 80). The surface pressure was investigated at the water–air interface using a Langmuir–Blodgett apparatus. Interfacial tensions at n-hexane–air and water–n–hexane interfaces were measured by a du Nouy tensiometer. The effects of different surface-active agents and their concentrations on the interfacial properties of surfactant films were determined. With saturated sorbitan monoesters the lengthening of the hydrocarbon chain increases the collapse pressure and molecular area at the water–air interface. Unsaturated Span 80 had a lower collapse pressure and a larger molecular area than its saturated counterpart Span 60. Under compression–expansion cycles, all sorbitan monoesters showed hysteresis effects. At the n-hexane–air interface there were no differences in the interfacial tension between different sorbitan monoesters. At the water–n-hexane interface, differences in CMCs were small, but the surface excess of Span 80 was markedly smaller and the molecular area larger than the corresponding values of other sorbitan monoesters.