A series of polyethylene oxide (PEO)/starch blends were prepared by extrusion and their films were prepared by compression molding. It was observed that the presence of characteristic peaks of PEO and starch at 845 and 1643.7 cm-1, respectively, in FTIR spectra of PEO/starch blends favors the blending of PEO/starch. The physicomechanical and optical properties of PEO/starch-blended films were measured. The tensile strength of the blended films decreased, whereas the haze values increased with an enhanced starch concentration in PEO/starch blends. The results obtained were correlated with microstructural parameters such as, crystallite size and lattice strain determined using wide angle X-ray scattering (WAXS) data. The X-ray line profile analysis shows that the crystallite shape area is maximum in PEO and decreases with the addition of starch. (C) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013