By expanding the inorganic framework of lead-halide perovskites to accommodate electron-accepting organic molecules, we realized an electronic structure in which a conduction band composed of localized molecular orbitals coexists with a dispersive valence band derived from the lead-halide framework. This unusual band structure, distinct from that of conventional halide perovskites, enables electrons and holes to reside in the organic and inorganic components, respectively, while retaining fundamentally different electronic characteristics.

　We have also demonstrated that the coordination environment of Pb(II) can be controlled through the design of molecular anions. By preserving the isotropic character of the Pb 6s orbital while selectively promoting its interaction with molecular orbitals, we achieved the coexistence of a wide band gap and a highly dispersive valence band. This study further revealed that not only the energy levels of molecular orbitals, but also their orbital symmetry and topology, are key design parameters governing the band structures of hybrid solids.