Polymer blend thin films have been paid great attention to technological applications including adhesion, coatings, liquid crystal alignment, electronics, optics, biotechnology, and sensors. In this thesis, I investigated the effect of supercritical CO2 (scCO2) as a green solvent for poly(ethylene oxide)/polystyrene (PEO/PS) blend thin films. We prepared a series of PEO/PS blend thin films with different PEO compositions thickness ranging from 20 nm to 50 nm. As a control experiment, we also processed the same PEO/PS films at high temperature (150 ??C) under vacuum. Comparison of these experimental results by using atomic force microscopy and optical microscopy clarified the significant plasticization effect of scCO2 on the phase separation, crystallization of PEO, and the swelling behavior of PS.