As an effective way to explore controlled nuclear fusion, laser inertial confinement fusion (ICF) is expected to obtain clean and pollution-free energy. Thin-walled polystyrene (PS) hollow microspheres are a type of microspheres urgently needed in ICF physics experiments. Thin-walled hollow microspheres are easy to crack while drying and being used due to the increase in diameter-to-thickness ratio (diameter/wall thickness). In this work, the influence of the PS materials on the quality of thin-walled microspheres was studied, and the mechanism was discussed. The results show that when the oil phase (PS) mass fraction was 4%, the stability of W1/O/W2 composite emulsion particles gradually increased with the increase of oil phase viscosity; when the oil phase mass fraction was not less than 8%, the stability of compound droplets was fine. There is no significant difference in the surface roughness of the corresponding microspheres. The sphericity and wall thickness uniformity of microspheres decreased with the increase of initial oil phase viscosity. In the drying process, the cracking rate of microspheres decreased with the increase of oil phase viscosity. The rate of microsphere cracking decreases as the mechanical properties of the raw material improves. To compensate for the adverse effect of the increase in oil phase viscosity on the sphericity and uniformity of the wall thickness of the microspheres, fluorobenzene (FB) droplets were introduced into the external water phase to reduce the solidification rate.