The elaboration of new Langmuir-Blodgett (LB) films containing Prussian blue and a surfactant derivative of the ruthenium tris(bipyridine) complex using a semi-amphiphilic approach is described in this paper. The redox and photoelectrochemical properties of these hybrid lamellar materials have been studied in aqueous KCl solutions. Dependencies of the cyclic voltammetry response on the number of deposited layers and the scan rate demonstrate that the hybrid LB films can be considered as a quasireversible system with a finite diffusion space. A large cathodic photocurrent is recorded when the LB films are irradiated with polychromatic light at a negative applied potential, indicating that both PB and the derivative of ruthenium tris(bipyridine) complex play an important role in the light-energy conversion process. A linear dependence of the cathodic photocurrent response on the number of deposited layers has also been exhibited and should be correlated to the presence of structural defects in the multilayers.