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A thin aqueous film prepared by layer-by-layer assembly of oppositely charged polypeptides on 4-aminobenzoic acid modified porous reticulated vitreous carbon (RVC) electrodes was used with the aim of forming a 3D-ITIES. The film containing a redox mediator, namely ferri/ferrocyanide, was placed in contact with an organic solution 1,2-dichloroethane containing an electron acceptor, 7,70,8,80-tetracyanoquinodimethane (TCNQ). The reduction of TCNQ was studied to characterise the electrochemical properties of the supported ITIES. When the film is dye-sensitised, a reduction photocurrent was observed upon illumination. This photocurrent was an order of magnitude larger than that measured on a planar electrode.