Atomic arrangements, substitution patterns, and properties of BN-doped C60 fullerene have been investigated using semiempirical MNDO and density functional theory (B3LYP/3-21G). The BN units prefer to stay together following “hexagon−hexagon junction”, “N-site attachment”, “hexagon filling” and “continuity” rules; this characteristic of atomic arrangement is independent of the compositions of BCN fullerenes. Charge redistributions after each BN substitution seem to play a guiding role for selecting the next carbon pair to be replaced by BN. The incoming BN group seeks the most highly charged carbon pairs. Up to twenty carbon pairs of C60 may be replaced by heteroatoms. The band gap (HOMO−LUMO gap) strongly depends on the number of BN units and their filling patterns. BN-substitution increases the electron donation capacity of fullerene.