We investigated the structural evolution of Polystyrene films at various conditions through multi-wavelength ellipsometry. We studied the thickness of film dependent of the process of swelling/shrinking, and the influence of the intensity of atmosphere,combining with PM (polarization microscope) to characterize the surface morphology. Results indicated that the increase and reduction of the film thickness are non-linear. Maximum swelling ratio and the variation of film thickness depend on the initial thickness of film and the intensity of atmosphere. Furthermore, the results demonstrated that in-situ multi-wavelength ellipsometry is an unique means to investigate the behavior of swelling and shrinking of film.