Surface modifications are often required to enhance cell adhesion and growth around implanted biomaterials. This study compares various functionalization processes in their ability to create high densities of oxygen- and/or nitrogen-containing functional groups, mostly on a polymeric biomaterial, polyethylene terephthalate (PET). Primary amine (NH2)-rich surfaces were prepared by low-pressure plasma-polymerization (L-PPE:N), plasma modification (functionalized PET, 'PETf'), chemical vapour deposition (Parylene diX AM), and grafting of polyallylamine (PAAm). Plasma polymerization was also used to obtain oxygen-rich (L-PPE:O) as well as hybrid (L-PPE:O,N) films, which were respectively compared to oxygen-rich tissue culture polystyrene (TCP) and hybrid (Primaria™) culture plates. Compositions and bond types were studied by X-ray photoelectron spectroscopy. Finally, the effect of each surface on cell adhesion and growth was assessed using human umbilical vein endothelial cells (HUVECs). Amine-containing surfaces manifested a wide [NH2] range, up to 8.9%. Hybrid surfaces, Primaria™ and L-PPE:O,N, showed lower [NH2] in spite of high [N], suggesting more varied and complex functionalities. Except for Parylene, all O- and NH2-rich surfaces promoted HUVEC adhesion and growth similarly, despite differing chemical compositions. Primaria™ showed the best cell behavior, but L-PPE:O,N did not reproduce this apparent synergistic effect. To conclude, both N- and O-rich surfaces displayed good cell-colonization properties, particularly plasma polymers, while 'hybrid' surfaces appear somewhat ambiguous and call for further investigation.