The skylight polarization models can simulate the polarization state distribution of the skylight, and are key tools to study the quantitative relationship between the polarization state distribution of the skylight and the characteristic parameters of the atmosphere. A skylight polarization model of various weather conditions was modelled, which based on adding and doubling method for solving the radiative transfer equation and T matrix method for calculating the scattering properties of particles. The comparison between the simulation results of this model and the calculation results of Hovenier et.al showed that more than 95% points’ relative error is less than 5%. The measurement experiment results with the polarization imaging system based on LCVR showed measurements are most consistent with the simulation results in degree of polarization in 80% of the area. It can be concluded that the model can accurately simulate the distribution of the polarization state of the sky light under various weather conditions.