The　design　and　synthesis　of　two　semiconducting　bis　(4-ethynyl-bridging　1,　8-naphthalimide)　bolaamphiphiles　(BENI-COO−　and　BENI-NH3+)　to　fabricate　supramolecular　metal–insulator–semiconductor　(MIS)　nanostructures　for　biomimetic　hydrogen　evolution　under　visible　light　irradiation　is　presented.　A　H2　evolution　rate　of　ca.　3.12　mmol　g−1⋅h−1　and　an　apparent　quantum　efficiency　(AQE)　of　ca.　1.63　%　at　400　nm　were　achieved　over　the　BENI-COO−-NH3+-Ni　MIS　photosystem　prepared　by　electrostatic　self-assembly　of　BENI-COO−　with　the　opposite-charged　DuBois-Ni　catalysts.　The　hot　electrons　of　photoexcited　BENI-COO−　nanofibers　were　tunneled　to　the　molecular　Ni　collectors　across　a　salt　bridge　and　an　alkyl　region　of　2.2–2.5　nm　length　at　a　rate　of　6.10×108　s−1,　which　is　five　times　larger　than　the　BENI-NH3+　nanoribbons　(1.17×108　s−1).　The　electric　field　benefited　significantly　the　electron　tunneling　dynamics　and　compensated　the　charge-separated　states　insufficient　in　the　BENI-COO−　nanofibers.　©　2020　Wiley-VCH　GmbH