Electronic wave function delocalization in a molecular material is highly surprising and desirable in the emerging field of molecular electronics.Here, we describe a new paradigm for molecular conductivity mediated by the strong intermolecular hybridization of a hollow core-bound molecular states in chemisorbed C60 molecular assemblies.In one-dimensional (1D) C60 wire and 2D C60 island,low-temperature scanning tunneling microscopy (LT-STM) revealed extensive, isotropic wave function delocalization at energy above 3.5eV, in contrast with the poor intermolecular wave function overlap of the lower energy π-molecular orbitals.Plain-wave density functional theory (DFT) indicates that a new kind of molecular orbital, which is derived from the central potential of the hollow cage shape of C60molecules, is responsible for this nearly-free-electron (NFE) like wave function delocalization.DFT calculations reveal that within the hollow C60 core there exists a central potential derived from the screening interaction (the exchange-correlation hole) and the σ-π orbital hybridization induced dipole on the surface of the C atom shell.This central potential gives rise to s, p, d, etc., symmetry atom-like orbitals, which we dub the superatom molecular orbitals (SAMOs), Both the experiment and theory show how these atomlike orbitals hybridize into H2 molecule-like σ and π symmetry bonding and antibonding orbitals of C60 molecular dimmers, and for larger aggregates, into 1D quantum wire and 2D quantum well bands with alkali atom-like NFE dispersions.Calculations also indicate that placing an alkali atom within a C60 molecule can bring down the SAMO energy to a scale of interest for the molecular electronics.As a common consequence of a hollow topology, we expect that similar SAMO states will exist in other molecules derived by wrapping and rolling molecular sheets into hollow cages and nanotubes.Thus, the existence of core bound states in such materials, and the possibility of exo and endohedral doping may lead to the discovery of molecular materials with NFE transport properties.