Using the wet-chemistry technique, we selectively reduced the surface of the PEEK film (PEEK-OH), and covalently fixed hexamethylene diisocyanate by addition onto the hydroxyl functions. The resulting PEEK-NCO film displayed free isocya nate termini, the basic hydrolysis of which gave the PEEK-NH2 film in 85% extent of derivatization. The PEEK-NCO film reacted with trifluoroethylamine in toluene, trifluoroethylamine in PBS buffer, GABA, and lysine in PBS buffer to furnish, respectively, the PEEK-CF3(A), PEEK-CF3(B), PEEK-CO2H, and PEEK(NH2)CO2H films in 80%, 45%, 30%, and 25% extents of derivatization, as determined from the F/C and N/C atomic ratios recorded in the corresponding XPS spectra. The surface reactivity of the PEEK-NH2 and PEEK-NCO films was assayed by coupling with appropriate H-3 labels followed by liquid scintillation counting of the sample-associated radioactivity. The PEEK-NH2, PEEK-CO2H, and PEEK-(NH2)CO2H films were used as substrates for the cultivation of CaCo2 epithelial cells; the presence of surface amine and carboxyl functions significantly improves the cellular adhesion and growth.