Photoelectrical rectifying property of biomolecular heterostructures is investigated in molecular scale. Recombinant ferredoxin and chlorophyll a were used as an electron acceptor and a sensitizer respectively in the molecular layer by mimicking photosynthesis. A self-assembled monolayer of recombinant ferredoxin was formed on Au surface, and then chlorophyll a was deposited onto the recombinant ferredoxin layer by Langmuir-Blodgett method. The formation of recombinant ferredoxin/chlorophyll a hetero-layers was confirmed by the SPR (surface plasmon resonance) spectroscopy, and the surface was observed by the STM (scanning tunneling microscopy). The rectifying property by the STS (scanning-tunneling-spectroscopy) based current-voltage characteristics was achieved in the recombinant ferredoxin/chlorophyll a hetero-layers. Thus, proposed hetero-layers functioned as a rectifier that can be useful property for the development of molecular-scale bioelectronic devices.