The extended Hückel method and the Green’s function method were used to calculate the electronic structure and electrical transport of Au electrode-C60, 2C60 or 4C60 fullerene-Au electrode systems. Furthermore, their electronic structure and electrical transport characteristics were compared and analyzed. The results show that (i) owing to the contact with the Au electrodes, the C60, 2C60 and 4C60 molecules change in their electronic structures significantly, and their energy gaps between LUMO and HOMO are narrow; (ii) the bonding between C60, 2C60 or 4C60 fullerene and Au electrodes is partially covalent and partially electrovalent; and (iii) the conductance of the three fullerenes conforms to the order of C60 > 2C60 > 4C60.