Layers of poly(3-hexylthiophene), PHT, phenyl vinyl thiophene, PVT3, poly(p-phenylene-2,3′-bis(3,2′-diphenyl)-quinoxaline-7-7′-diyl), PPQ, and covalently linked porphyrin−fullerene donor−acceptor dyad, P−F, were deposited as various multilayer films, which then were used to study photoinduced electron transfer and photocurrent generation. The aim of the research was to clarify functioning of different energy and electron donating and accepting layers in charge transfer processes, which were initially created in a film consisting of parallel P−F molecules. The reactions were studied by means of time-correlated and steady-state fluorescence, time-resolved photovoltage, and electrochemical photocurrent measurements. The longest-lived charge-separated state and the highest efficiency of photocurrent generation were obtained for the multilayer structure of PHT|PVT3|porphyrin−fullerene. Porphyrin−fullerene dyads deposited parallel as the Langmuir –Blodgett film transfer electrons from porphyrin to fullerene yielding radical cation and anion moieties, respectively. The dyad on a PHT layer induces electron donation from PHT to the porphyrin cation. When PVT3 is deposited between the PHT and the P−F layers, it promotes both energy and electron transfer to the porphyrin moiety of the dyad, retards the recombination of the primary charge-separated state, and thus increases the photocurrent generation. PPQ was used as an electron acceptor from the fullerene radical anion, causing an increased lifetime of the charge separation.