The optical properties in the middle infrared of pyrosolyn-based films on glass and, silicon substrates were investigated by spectroellipsometric method realised in the Beattie-Corm scheme using Fourier transformation spectrometer. These thin dye films are found to be rather anisotropic due to perceptible singularity in ellipsometric parameter spectra at the wave number of 1250 cm−1and its red-shifted distinct fine structure. The behaviour of this singularity being registered by the film-substrate and substrate-film side probing is shown to depend on such technological parameters as a distance between a vaporiser and a substrate, the temperature of a glass substrate and the pressure of vapour of volatile components of dyes. The estimation of the thickness d of the dye films formed on a glass substrate by solution of inverse ellipsometric task is efficient at d∼100 nm. The recording surface structure acquired by using the second harmonic radiation of Nd-laser at its power of the order of 10 mWt during recording in a pit form was investigated by means of scanning tunnel microscopy.