A method has been developed to determine orientation distribution function (ODF) of anisotropic paramagnetic species by analysis of the angular dependence of the ESR spectra. The method is based on computational spectra simulation. The ODF is represented as an expansion in terms of orthonormal functions. The expansion coefficients are determined through minimization of discrepancies between simulated spectra and experimental ones. By means of the suggested method we have determined the orientation distribution functions for radical probe 2,2,6,6-tetramethyl-4-ol-piperidinooxyl in 4-n-amyl-4'-cyanobiphenyl aligned by magnetic field and 2-septadecyl-2,3,4,5,5-pentamethylimidazolidine in polyethylene stretched films. In each case, thermal evolution of the ODF has been investigated.