Molecular level studies of the structure and mechanical properties of polymer surfaces have been carried out by sum frequency generation (SFG) surface vibrational spectroscopy and atomic force microscopy (AFM). The surfaces of different grades of polyethylene and polypropylene have been characterized—including during the glass transition and when mechanically stretched. Copolymers that have hard and soft segments with different glass transition temperatures show phase separation, an effect of hydrogen bonding between the hard and soft segments, that influences their adhesive and friction properties. AFM and SFG show that low surface energy additives migrate to the surface and alter the surface mechanical properties. Polymers, where the chemical nature of the end groups is different from the backbone, show surface segregation of the hydrophobic part of the chain in air and the hydrophilic part in water. Likewise, in miscible polymer blends, surface segregation of the more hydrophobic component in air and the more hydrophilic component in water is observed. This area of surface science requires increased attention because of the predominance of polymers as structural materials and as biomaterials.