Scanning electrochemical microscopy has been used in combination with a specially designed Langmuir trough to compare the kinetics of oxygen transfer across an L-alpha-phosphatidylethanolamine, distearoyl monolayer spread at three different interfaces: air/water, air/water in contact with an oil lens, and oil/water. The monolayer is shown to reduce the kinetics of interfacial transport, and rate constants for the transport of oxygen across each interface, at different surface pressures, have been evaluated. The results obtained for each interface are compared, and the implications for studies of passive diffusion across cell membranes are discussed.