In this paper, we investigate the effects of shape distribution of aerosol particles on the volumetric scattering properties, as well as the radiance and polarization distributions of skylight, by numerical simulations. The results demonstrate that the shape distribution indeed exerts a significant influence on the skylight degree of linear polarization. The skylight polarization calculated assuming the microscope-measured shape distributions is distinct from that using the inversion-based shape distributions. The significant effects will influence the retrieval of the sphericity of aerosols based on the sun-sky radiometer measurements. Our results suggest that using representative shape distributions obtained by direct microscopic observations of aerosol samples captured in the natural atmosphere has a high potential to improve the retrieval of the aerosol shape parameter.