Nitrogen (N)-rich organic thin films were deposited using both low-pressure plasma- and vacuum-ultraviolet-based techniques, from mixtures of ammonia (NH(3)) and ethylene (C(2)H(4)). These films were investigated using angle-resolved and excitation energy resolved X-ray photoelectron spectroscopy (ARXPS and ERXPS, respectively) in order to determine their sub-surface chemical profiles. These two techniques enable one to tune the "XPS 95%" information depth, z (95%), by varying either the angle or the excitation energy. Using a combination of both techniques, z (95%) can be varied continuously from 0.7 to 11 nm. The surface-near chemistry is investigated using both high-resolution C 1s spectra and elemental concentrations derived from elemental peak intensities. Results show that while laboratory XPS, and even ARXPS, suggest homogenous surface chemistries, the novel combination of ARXPS and ERXPS points to the existence of a compositional profile in the extreme outer surface layer. Our conclusions are supported by simulations using SESSA software.