Theoretical as well as experimental investigations were carried out for the propagation of leaky waves along an important class of optical thin‐film waveguides. For this type of guiding structure which may consist of heteroepitaxial deposition of ZnS or ZnSe on GaAs, the dielectric constant of the thin film is less than that of the substrate. Consequently, only the leaky type of guided waves may exist. Theoretical results show that the attenuation constants of leaky modes, which may be TE or TM, are inversely proportional to (thickness of layer)3and directly proportional to (wavelength)2, and that TM modes are more lossy than TE modes. The existence of these leaky modes has also been demonstrated for three different thicknesses.