The effects of different functionalized polypropylene (PP) and diethyl maleate (DEM) combined with styreneethylene-butene-styrene copolymer (SEBS) on various properties of extruded-stretched films of polypropylene/ethylene vinyl alcohol (PP/EVOH) blends were studied. The stretched films of the original PP/EVOH blends and those of the polymer-g-DEM modified blends showed lamellar-type morphology, whereas their maleic anhydride (MAH) functionalized counterparts showed fibrillar morphology. Such peculiar morphology resulted in a dramatic decrease of oxygen permeability as compared with the unmodified or MAH modified PP/EVOH blends. These spectacular improvements in barrier properties were obtained without much altering thermal and mechanical properties of the blend.