The conformation and orientation of polymer chains at surfaces and in thin films can play an important role in determining the properties of technological systems, and may be different from the bulk polymer. Techniques such as GIXS, NEXAFS, AFM, infrared spectroscopy, ellipsometry and XPS are currently being used to investigate the arrangement of polymer chains at surfaces. Conformational effects in the XPS spectra of polymers are small, but advances in instrumentation over the past decade have increased their probability of detection. The search for conformational signatures requires careful measurements on well characterised polymers as a function of conformational change. Changes in conformation often accompany a change in crystallinity or physical state. Polymers suffer x-ray induced degradation during XPS which can mask subtle conformational effects. Hence time dependent studies are required to establish upper limits on x-ray exposure times such that degradation is not a concern. Differential charging can also mask subtle spectroscopic effects and good charge compensation is crucial for the detection of conformational signatures. Orientation effects in polymer systems can be probed by angle dependent XPS studies. A conformational signature in the C 1s spectrum of PET will be discussed and comparison of XPS and infrared data will be used to demonstrate faster conformational change at the surface than in the bulk when the polymer is annealed above Tg. Conformational signatures in the valence bands of PEG, PTMG and nylon 12 will also be described. Angle dependent XPS studies of orientation effects in molecular overlayers on PTFE tribological transfer films will be discussed. Functional group orientation effects in acrylic polymers will also be described.