We present a simple method to measure the degrees of circular polarization (DoCP) of laser light inside a vacuum chamber and the birefringence of a vacuum window by detecting the fluorescence emitted by Doppler cooled ions in an ion trap. Imperfect laser polarization will cause ions to be pumped to the dark state which will decrease the fluorescence rates of the ions. With a simulation based on the rate equations of the relevant energy levels of 25Mg+ ions, we find that the fluorescence rate is sensitive to the DoCP of the laser. Based on the simulation result, we present a new method to optimize the DoCP of the laser inside the vacuum chamber by adjusting fast axis azimuthal angles of a half-wave plate and a quarter-wave plate outside the vacuum chamber. The laser light is optimized to be circularly polarized with an uncertainty of the DoCP of 7.8 × 10-5. With the obtained polarization information on both sides of the vacuum window and treating the vacuum window as an unknown wave plate, the phase delay and the fast axis azimuthal angle of the vacuum window can be determined in the form of Mueller matrix. The phase delay is determined to be 197.60(39)°, and the fast axis azimuthal angle is determined to be 104.00(5)°.