Ultrafast photoinduced electron transfer (PIET) dynamics of a C70-encapsulated bisporphyrin covalent organic polyhedron hybrid (C70@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 Å), without the aid of covalent bonds. Sub-picosecond PIET (τET ≤ 0.4 ps) and very slow charge recombination (τCR ≈ 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 (λ ≈ 0.18 eV), induced by the intrinsic structural rigidity of the C70@COP-5 complex.