The application of electrochemical techniques to the characterization and doping of Langmuir-Blodgett (LB) films of the amphiphilic N-octadecylpyridinium-Ni(dmit)(2) complex, in solution and in LB film form, is discussed, A stable cyclic voltammetric response consistent with solution electrochemistry was found for both monolayer and multilayer films in KCI aqueous electrolyte. Electrochemical doping increased the d.c. conductivity of the LB films by up to six orders of magnitude. In this way, stable, in-plane, room temperature conductivity values of 3 x 10(-2) S cm(-1) were achieved.