X-ray photoelectron spectroscopy (ESCA) has proved the single most powerful tool for investigation of organic based polymer surface structure. This article begins by delimiting the various data levels and experimental parameters available from the ESCA experiment and noting how these information levels can be used to study the time and temperature dependent behavior of polymer surface phenomena. These include absolute binding energies, photon energy dependent studies, angular dependent studies, and sample charging. The application of ESCA in migration phenomena, plasma synthesis of ultra thin fluoropolymer films, and in the investigation of the surface chemistry of the nitration and denitration of cellulose materials are then described. Discussion of the latter application includes an introduction to the history of nitration of cellulose. Foundations for the production methods used for nitrocelluloses were largely laid down in the early twentieth century. Until recently, investigation was limited to bulk properties. In a heterogeneous material, the surface provides a window on the reaction. Thus, experimental work conducted by the author was a comparison of surface and bulk nitration and denitration of cellulose materials. It was found that sulphate esters are formed in the very surface regions, with virtually none formed at depth.