Abstract Localized molecular orbitals (LMOs) have been calculated for C60 and C70 by using the CNDO/2 approximation and the energy-localization scheme of Edmiston-Ruedenberg. It is found that the π-bonding on the surfaces of the spherical carbon cages is localized into two-centered two-electron (2c2e) and three-centered two-electron (3c2e) bonds with additional charge distributions delocalized in the neighboring atoms. The localized electronic structures, the hybridized states of carbon atoms, the spherical aromaticity, and the reactivity for forming metal complexes of C60 and C70 are discussed.