Wide-angle X-ray diffraction (WAXD) and the scanning electron microscopy (SEM) were used to determine the morphology of crystalline phase of blends of poly(ethylene-oxide) (PEO) and styrene-acrylic acid (S-AA) copolymers neutralized with sodium ions (Na+). In this study, we investigated the effects of blend composition and the content of ionic groups in amorphous ionomers on the degree of crystallinity and the crystallite sizes. It was found that the degree of crystallinity of PEO in the blends decreases both with increasing S-ANa(6.4) content and with increasing ANa content. The sizes of PEO crystallites, measured both in the direction perpendicular and parallel to the polymer axis, are almost independent of ionic groups content in the amorphous component of the blends but they decrease with increasing S-ANa(6.4) content. For the blends containing small amounts of PEO the confined crystallization of this polymer were observed. The final crystalline morphology of these blends, observed by SEM method, is different in comparison to that formed without spatial confinement.