Langmuir-Blodgett films were studied using a variable energy slow-positron beam. We measured the energy spectra of positron annihilation radiation for Cd and Mg eicosanoid films and obtained the V- and S-parameters as a function of the incident positron energy, E. In the V-E curves of Cd eicosanoid films, there were dips at the positron energy whose mean implantation depth corresponding to the first and second Cd 2 + layers from the surface. These dips are interpreted as the result of inhibition of Ps formation by the Cd 2 + ions. The S-parameter was found to be sensitive to chemical composition of the film and also to possible structural change due to heat treatment. Our results suggest that positron beams provide valuable information about the microstructure of the Langmuir-Blodgett films.