We have considered some well-known methods of measuring the refractive index in order to determine how the surface layer affects measurement results. We have proposed a new and relatively simple method in which the surface layer contributes considerably less to the formation of the resultant beam than the bulk material. This method makes it possible to more correctly determine values of the refractive indices of a bulk material. With this method, one can determine not only the relative value of the refractive index but also its absolute value. We have shown that quartz can be efficiently used as a substrate in the ellipsometric determination of optical constants of metal, semiconductor, and dielectric films. Our results are very important for research on the physicochemical properties of metal or semiconductor films rapidly oxidizing in air atmosphere.