Poly (methylmetacrylate)-Poly(ethylene oxide) (PMMA-PEO) polymers blend films were prepared using the solution casting method. The polymer thin films were characterized by X-ray difraction (XRD), Scanning Electron Microscopy (SEM), FTIR and differential scanning calorimetry (DSC) technique. The amorphous or crystalline nature of polymers has been confirmed by XRD analysis. The PMMA surface morphology shows rough surface and micro pore structure. Appearance of rough surface in SEM micrograph of pure PEO was suggested several crystalline domains. The surface morphology changes severely when PEO added to PMMA polymer, which shows the development of surface morphology from smooth to rough with increasing of PEO concentration in PMMA. FT-IR data shows that some of the bands found to be shifted and intensities of some of the bands are decreased and some are disappeared with the addition of PEO to PMMA when compared to pure PMMA and PEO, which suggests the coordination/ interaction between PMMA and PEO matrixes. DSC results showed that the melting temperatures (Tm) of PMMA and PEO blend decreases when compared to pure PEO, PMMA.