New hybrid Langmuir-Blodgett (LB) films containing Prussian Blue have been studied by cyclic voltammetry and electrochemical impedance spectroscopy. The dependencies of the cyclic voltammetry response on the number of deposited layers and the scan rate are described and show that the hybrid LB films can be considered as a quasi-reversible system with a finite diffusion space. On the basis of the impedance spectroscopy results, the charge transport process through the lamellar materials is modeled with an equivalent circuit considering two kinds of charge transport. The diffusion coefficients associated with the motions of the charged species are found to be very small, reflecting the fact that the insulating lipid layers considarebly hinder the diffusion of the charged species.