Abstract: The binary cluster anions of Ge/Sn, Ge/Pb, Sn/Pb, Co/Ge, Co/Sn and Co/Pb binary cluster ions, produced by direct laser ablation, were studied with a Tandem TOF mass spectrometer. The experiments show that E1/E2 (E1/E2 denotes Ge/Sn, Ge/Pb and Sn/Pb) binary clusters dominantly distribute in the lower mass region, in which the number of heavy atom is much larger than that of light atom. And composition and distribution of these binary clusters indicate that their structures and properties are similar to those pure group-14 elements cluster. By laser ablating the mixtures of transition metal cobalt and group-14 elements, mass spectra showed that abundance Co/E (E denotes Ge, Sn and Pb) cluster formed in higher mass range. Magic number CoGe10－, CoSn10－ and CoPb10－ may have bi-capped tetra nal antiprism structure and is icosahedral structure. The difference between E1/E2 and Co/E binary cluster anions shows that all atoms for E1/E2 binary cluster anions are on the framework of the cage, while the cobalt atom for Co/E binary cluster is inside the cage of E.