Surfaces of polyethylene and polyimide films were treated in NH3and N2plasma using ‘‘dual‐frequency’’ excitation: The samples were exposed to a microwave (2.45 GHz) glow discharge, while variable radio frequency (13.56 MHz)—induced negative direct current bias voltage values were simultaneously applied. The surface chemical structure was determined by high‐resolution x‐ray photoelectron spectroscopy. Up to 40 at. % of nitrogen was incorporated onto the sample surface by exposure to a microwave discharge in N2, while systematically lower N uptake was found in NH3plasma. Nitrogen was found to be bonded predominantly in amine (C–N) groups by NH3‐type plasma, and in imine groups (C=N) by N2plasma. Surface ‘‘damage’’ of polyimide, including opening of benzene rings and breaking of carbonyl groups, accompanied by the formation of increasing concentrations of chemically reactive receptor sites, has been demonstrated with increasing the energy of bombarding species.