The understanding of surface bonding and composition of complex polymer mixtures used for biomedical implant materials can be accomplished by a combination of techniques. In this study, vibrational spectroscopic probes of bulk and surface bonding and composition are combined with measurements with angular dependent X-Ray Photoelectron Spectroscopy (XPS or ESCA). These data provide a detailed description in the surface composition of Biomer and Avcothane, commercially available biomedical grade polymers and model systems polydimethylsiloxane (DMS) and Avcomat, all of which have been cast as smooth films from solution. Impurities are observed segregated in the near surface region sampled by ESCA which are not observed in the surface infrared results. Both Attenuated Total Reflectance (ATR) and Photoacoustic (PA) sampling are utilized, ATR to provide a depth profile and demonstrate the higher surface sensitivity of PA sampling. The combined results describe the depth of segregation of DMS blocks in Avcothane, the presence of DMS within the topmost 20 A in Biomer, and similar impurities in the model polymers. These results point out the need for multitechnique approach and the control of sample preparation and morphology in understanding complex polymer surfaces.