The surface compositions of two biopolymer blends, Biospan-SP/Phenoxy (BSP/PHE) and Biospan-F/Phenoxy (BF/PHE), have been studied using sum frequency generation (SFG), X-ray photoemission spectroscopy (XPS), and contact angle goniometry. BSP and BF are polyurethanes capped with poly(dimethylsiloxane) (PDMS) and fluoroalkyl (-(-CF2-)(n)-) as end groups, respectively. With contact angle goniometry, the surface tensions of pure BSP, BF, and PHE were found to be 26, 16, and 45 dyne/cm. For each of the blends, the polymer component with a lower;surface tension (BSP or BF, not PHE) tends to segregate to the surface. Our SFG experiment shows that the surface concentration of the surface-active component increases sharply as its bulk concentration increases. For BSP/PHE land BF/PHE) in air, the surface of the polymer blend is fully covered by BSP land BF) at a bulk concentration of 3.5 wt % (and 1 wt %). The contact angle measurements and the XPS studies yield compatible results. Comparison of results for BSP/PHE, BS/PHE (published before(1)), and BF/PHE polymer blends shows that the lower the surface energy of the surface-active component (surface tension: BF < BS ( BSP), the easier it is for the component to segregate to the surface (the minimum bulk concentration to saturate the surface is BF (1 wt %) < BS (1.7 wt %) < BSP (3.5 wt %)). After exposure to water, SFG spectra indicate that the surface layer of a polymer blend could be restructured. For BSP (3.5 wt %)/PHE, the hydrophobic end groups of BSP submerge while the hydrophilic polyurethane backbone emerges. For BF (1 wt %)/PHE, PHE emerges at the surface after exposure to water, but for BF (5 wt %)/PHE, the BF component dominates the surface in both air and water. Our results demonstrate the bifunctionality of polymer blends and show that the surface chemistry of polymer blends may be dominated by a minor component, while the mechanical stability of the polymer is controlled by the major component.