Novel bis(perfluorophenyl azides) coupling agents, containing spacer arms from ethylene or ethylene glycol subunits, were successfully synthesized. Nitrenes photogenerated from these novel bis(PFPA) coupling agents were applied successfully to the cross-linking of poly(ethylene oxide) (PEO(10.000)) in either aqueous medium or at the solid state, thus, we demonstrated the potential of these bis(PFPA) molecules as promising coupling agents in surface engineering. (C) 2011 Published by Elsevier Ltd.