This work describes the synthesis and study of two new hybrid (organic-inorganic) three-layered systems with improved semiconductive behavior. As far as the first system is concerned, CdSe-Fc-Zn (x) Cd1-x Se, the inner layer is CdSe, while the outer one is Zn (x) Cd1-x Se, both prepared by electrodeposition. The partial substitution of Cd by Zn in the outer layer leads to an environmentally friendlier product compared with those containing exclusively Cd. The organic layer of the hybrid system is ferrocene (Fc), which is enveloped between the two inorganic layers in a sandwich-like structure. Ferrocene is deposited on CdSe layer using the spin-coating technique. It was found that the as-prepared CdSe-Fc-Zn (x) Cd1-x Se system has improved properties and photoconductivity compared with the Zn (x) Cd1-x Se monolayers. In order to further enhance the photoresponse of the system described above, a second three-layer hybrid was developed, the CdSe-Fc-Zn (x) Cd1-x Se/oxalate. This system was produced with the electrodeposition of the outer layer Zn (x) Cd1-x Se in the presence of disodium oxalate, a selected organic additive in the bath. All the products were fully characterized via XRD, SEM-EDAX, band gap, and photoelectrochemical cell (PEC) measurements, and the results confirmed the development of the new hybrid semiconductive systems. The as-described CdSe-Fc-Zn (x) Cd1-x Se and CdSe-Fc-Zn (x) Cd1-x Se/oxalate systems, compared to the pure inorganic CdSe and Zn (x) Cd1-x Se thin films, present remarkably improved photoresponse due to the synergetic action of their components. [GRAPHICS] .