We perform in this paper a kinetic study of the photoelectrochemical responses of nanoporous thin photoactive films. The films were fabricated by by a layer-by-layer assembly of positively charged polyelectrolytes (poly-L- Lysine, pLys) and negatively charged semiconductor nanoparticles (NPs) on a carboxylic acid terminated alkanethiol-modified gold electrode. Two types of NPs were used to build uniform films: cadmium selenide (CdSe) and cadmium selenide/cadmium sulfide core/shell (CdSe@CdS). Large photocathodic and photoanodic currents were recorded for CdSe and CdSe@CdS sensitized films, respectively. A theoretical model of the photocurrent responses was developed to analyze the kinetics of photoinduced processes and coupled reactions, showing that the multilayer films behave as homogeneous nanoporous semiconducting photoelectrodes.