An approach for determining the optical constants of the weakly absorbing substrate is developed and applied to obtain the parameters of CaF2 and fused silica substrates in deep ultraviolet (DUV) and vacuum ultraviolet (VUV) range. A method for extracting the optical constants of thin films deposited on strongly absorbing substrate, which is based on the reflectance spectra measured at different angles of incidence, is also presented. The optical constants are determined by fitting the measured spectra to the theoretical models. The proposed method is applied to determine the refractive index and extinction coefficient (n, k) of MgF2 film deposited on silicon substrate by electron beam evaporation with substrate temperature 300 oC and deposition rate 0.2 nm/s. The determined n, k values at 193 nm are 1.433 and 9.1 \times 10-4, respectively.