In this paper, PS/PC blend film (about 120 microns thick) and PS/PMMA (about 90 microns thick) blend film were prepared by evaporation the solvent very slowly from polymer blend solution. Different FTIR methods were used to determine the composition distribution along the vertical direction of the films. PS/PC film was firstly sectioned by ultramicrotomy, then the vertical section was measured to determine the composition of every 16 microns width unit from the surface-side to the bottom-side by Microscopic transmission-FTIR. The results showed that the concentration of PS was significantly greater in the vicinity of the surface of the film than that in the bulk, i.e., the component of PS enriched to the surface. Focusing the reflecting infrared light on different layer of the film, we can detect the composition of the different depth region in the PS/PMMA blend film. As the result, PMMA aggregated to the bottom of the film. It was considered that this effect was related to the different affinity and wetting prosperities of the blend component to the substrate or air.