The results of numerical simulation of a nanodimensional film-transition layer-absorbing substrate structure are presented. It is found that the transition layer affects the accuracy of determining the refractive index and thickness of the nanodimensional coating. It is shown that the introduction of the effective values of the refractive index and absorption coefficient of the substrate improves the accuracy of ellipsometric measurements of the nanodimensional film parameters. Physical (full-scale) and numerical experiments demonstrate that, when the thickness and refractive index of a nanodimensional film on a substrate with an unknown transition layer comparable in thickness with the film are measured, it is appropriate to replace the substrate-transition layer structure by a substrate with effective optical parameters. It is found that a change in the thickness of the transition layer does not noticeably affect the accuracy of determining the thickness and refractive index of the film deposited when the effective values of the refractive index and absorption coefficient of the substrate are used.