The theory of infrared 45° reflectometry is revised and generalized to the case of anisotropic very‐thin films and heterostructures on substrate. We obtain approximate expressions for the difference Δ45= Rp — Rs2 between the reflectivity for p‐polarized light (Rp ) and the squared reflectivity for s‐polarized light (Rs2) at 45° angle of incidence. These results give a good interpretation of frequency spectra of Δ45 and allow to associate correctly the resonances in Δ45 with transverse and longitudinal optical phonons in anisotropic films. The application of the infrared 45° reflectometry to superlattices is discussed.