Complex structures based on "host-guest"' systems make possible the development of new materials with promising technological applications. In this work, we synthesized a V2O5. nH(2)O/surfactant (N-cetyl-N,N,N,-trimethylammonium bromide) composite that presented an improved charge capacity and stability on electrochemical response in relation with a V2O5.1.9H(2)O matrix. CTA(+) intercalated into the V2O5 lamellar structure favors the kinetics of V-IV/V-V solid-state redox transitions. Moreover, the spectroelectrochemical behavior was verified even after several successive redox cycles.