We investigated the electrochemical properties for Langmuir-Blodgett (LB) films of functionalized polyimide. LB films of polyimide monolayer were deposited by the Langmuir-Blodgett method on the indium tin oxide(ITO) glass. The electrochemical properties measured by cyclic voltammetry with a three-electrode system(an Ag/AgCl reference electrode, a platinum wire counter electrode and LB film-coated ITO working electrode) at various concentrations(0.5, 1.0, and 1.5 N) of NaClO4 solution. The current of reduction and oxidation range was measured from 1650 mV to -1350 mV, continuously. The scan rates were 50, 100 and 150 mV/s, respectively. As a result, monolayer and multilayer LB films of polyimide are appeared on irreversible process caused by the oxidation current from the cyclic voltammogram.