The transmittance models of single slab and two spliced slabs were built, and a new method to determine optical constants of materials was proposed based on inversing the transmittance spectrograms of single slab and two spliced slabs. The measurements of transmittance spectrogram of zinc selenide glass slabs with different thickness in the infrared wavelength range of 1.33~21 μm at normal incidence were investigated by Bruke V70 FTIR spectrometer. The optical constants of zinc selenide were achieved by the inverse methods. The results indicate that the optical constants of zinc selenide determined by the new inverse method are in good agreement with previous data sets.