Abstract: Detailed analysis is carried out to describe the non-uniform structure of sulfur doped monolayer for Polystyrene hollow microscopy. The results demonstrate that the appearance of this non-uniform structure comes from PSS (sodium polystyrene sulfonate, the doped sulfur agent). The film forming capability of PSS is also investigated with infrared image microscopy and polarizing microscope. PSS has a bad performance in film forming, and the ordering aggregates and crystal appear on the surfaces of the film. There is great differencein the thermal properties between the PSS film and the polystyrene film indicated by thermal treatment, and the PSS film is easy to have brittle crack and strip from the polystyrene film . Therefore, PSS is not appropriate for fabricating the hollow microspheres when the content of doped sulfur is high.