Highly ordered mesoporous silica thin films (MSTFs) were spin-coated on Si wafers by self-assemble of water-soluble nanocrystal micelles with soluble silica. The gold nanoparticles (GNPs) were assembled within the silica matrix. Based on this nanocomposite, nanoscale electrodes were fabricated to form single electron devices. Two main transport behaviors of resemblant Coulomb blockage were demonstrated in the current-voltage measurements. The Coulomb island size calculated from the current-voltage data was close to the real size of the GNPs. The random loading positions of GNPs in the MSTF, which lead to uncertain tunneling resistances, might be response for the conductive differences.