In this work, the polarization state of reflected light from anisotropic thin film is studied and measured when polarization conversion reflection becomes obvious. It is found that the polarization state measurement is a sensitive method to detect the optical constants of an anisotropic thin film. In experiment, the Magnesium fluoride film is prepared in a thermal coater. The optical constants include thickness, the columnar angle and three principle refractive indices can be measured by polarizer-sample-analyzer system. The sensitivities and errors of the measurement are discussed and optical constants can be detected precisely.