Two-component self-assembled films have been fabricated by codeposition of sulfur-derivatized poly(methyl methacrylate) (S-PMMA) and poly(ethylene oxide)(PEO). The unique surface morphology which results has been investigated by polarized infrared spectroscopy, contact angle measurements, and ellipsometry. In this binary blend, a coexistence of both PEO crystalline domains and an amorphous blended matrix was observed. Further investigation revealed that the PEO chains in the crystalline regions were oriented preferentially with their helical axes normal to the substrate surface.