Ultrafast photoinduced electron transfer (PIET) dynamics of a C-70-encapsulated bisporphyrin covalent organic polyhedron hybrid (C-70@COP-5) is studied in a nonpolar toluene medium with fluorescence and transient absorption spectroscopies. This structurally rigid donor (D)-acceptor (A) molecular hybrid offers a new platform featuring conformationally predetermined cofacial D-A orientation with a fixed edge-to-edge separation, R-EE (2.8 angstrom), without the aid of covalent bonds. Sub-picosecond PIET (tau(ET) <= 0.4 ps) and very slow charge recombination (tau(CR) approximate to 600 ps) dynamics are observed. The origin of these dynamics is discussed in terms of enhanced D-A coupling (V = 675 cm(-1)) and extremely small reorganization energy (lambda approximate to 0.18 eV), induced by the intrinsic structural rigidity of the C-70@COP-5 complex.