Zinc Protoporphyrin IX-based compound 1 connected with ruthenium tris-bipyridine and beta -cyclodextrin and its reconstituted Myoglobin(Mb(1)) were newly synthesized to construct covalently and non-covalently linked electron transfer reactions using semisynthetic protein. In the presence of an electron acceptor such as anthraquinone, Mb(1) can bind it on the surface and form a self-assembled donor-sensitizer-acceptor triad. The final charge separated state via stepwise electron transfer was generated after photo-excitation of the ruthenium complex by laser flash photolysis.