Plasma polymerized films of allylamine were surface derivatized in subsequent wet chemical processes using a diepoxy‐PEG linker to covalently bind different biomolecules that are known to influence cell adhesion. The initial attachment of human umbilical vein endothelial cells (HUVECs) was studied on (i) unmodified PTFE, (ii) PTFE modified with a layer of plasma polymerized allylamine (pp‐AA), and (iii) PTFE modified with a layer pp‐AA which was further modified using known adhesion molecules coupled to the functional surface via a linker molecule. Statistical analysis of the data initially show significant adhesion improvement of HUVECs on pp‐AA and on pp‐AA modified with either L‐RGD or C‐RGD in comparison to the bare PTFE. The statistical significances between the pp‐AA surface and the modified pp‐AA/RGD surface were however found to be negligible. A significant further improvement was observed for the modified surfaces derivatized with the very much larger fibronectin.