The chemistry of substrate-film interface (underside) of di(ethylene glycol) dimethyl ether plasma polymer (DGpp) films has been studied directly and compared to the top layer of the film (topside). By depositing the plasma polymer films onto indium tin oxide (ITO) glass, the films were easily delaminated from the substrate. The top- and underside of the films were examined by X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. It was found that a rapid increase in pressure during plasma polymerization results in steep chemical gradients in the films, while small pressure changes do not lead to chemical gradient formation. These observations validate the findings of previous neutron reflectometry modeling studies of this class of plasma polymer thin film. In addition, subtle variations in plasma polymer film chemistry were observed between different substrates they were deposited onto. This approach will allow additional studies on the mechanisms of early plasma polymer thin film formation with various monomers. (C) 2013 Published by Elsevier B.V.