The local wave function of π electrons is constructed according to the structural property of C60 molecules, and the hopping energies are calculated. For the unequal sp3 hybridization, when the effective nuclear charge number Z=1.112 the energy gap (LUMO-HOMO), bandwidth and ionization threshold (T3g-Hu) obtained by optimizing calculation are 1.70eV,12.19eV and 8.13eV,respectively, these coincide with the experimental results. The corresponding hopping energies are:-2.299eV and -2.113eV for the nearest neighbors; 0.103eV and 0.170eV for the next nearest neighbors; -0.036eV，-0.013eV and -0.005eV for the third neighbors. On the other hand, the computed result also reveals that there are a lot of Rydberg orbitals for C60 molecules.