We investigated the electrochemical properties for Langmuir-Blodgett(LB) films mixed with l-bromotetradecane(Cl4), l-bromohexadecane(Cl6), and l-bromooctadecane(Cl8). The alkyl bromides mixture was deposited by using the Langmuir-Blodgett method on the ITO glass. The electrochemical properties measured by using 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, 1.5 and 2.0 N) of NaClO4 solution. A measuring range was reduced from initial potential to -1350 m V, continuously oxidized to 1650 mV. The scan rate was 100 mV/s. As a result, LB films of Cl4, Cl6, and Cl8 mixture monolayers appeared irreversible process caused by only the oxidation current from the cyclic voltammogram. The diffusivity(D) effect of LB films decreased with increasing of alkyl bromides amount.