In this work, we report a new way of modifying an electrode by combining the intrinsic conductivity property of vanadium pentoxide xerogel with its water insolubility in the presence of the cationic surfactant N-cetyl-N,N,N,-trimethyl-ammonium bromide (CTA + Br - ). The obtained hybrid compound enables the immobilization of electroactive anions such as hexacyanoferrate (III) ([Fe(CN) 6 ] 3 - ) and its analogue pentacyanonitrosylferrate (II) ([Fe(CN) 5 NO] 2 - ), rather than cations.