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.