A model poly-epoxy surface formed by the reaction of DGEBA and EDA is studied by the combination of experiments and DFT calculations. A special synthesis protocol is presented leading to the formation of a surface that is smooth (S-a < 1 nm), chemically homogeneous, and that presents a low-defect density (0.21 mu m(-2)), as shown by AFM characterizations. Then, XPS is used for the determination of the elemental and functional groups' surface composition. DFT allows the identification and assignment of individual bonds contributions to the experimental Is core-level peaks. Overall, we demonstrate that such a model sample is perfectly suitable for a use as a template for the study of poly-epoxy surface functionalization. (C) 2014 Elsevier B.V. All rights reserved.