In this work, a new alpha-gamma-type [Mo8O26](4-) anion was first synthesized and characterized by single-crystal X-ray diffraction analysis and was obtained by introducing molybdate to the synthesis of metal-organic complex (MOC) under hydrothermal conditions. An octamolybdate-based MOC, namely, {[Cu-8(H2O)(6)](dpyh)(4)(alpha-gamma-Mo8O26) }center dot(beta-Mo8O26)center dot 8.5H(2)O(H(2)dpyh = N,N-bis(3-pyrazolamide)-1,2-hexahydrobenzene), was obtained. The alpha-gamma-type [Mo8O26](4-) anion was composed of four MoO6 octahedra and four MoO s trigonal bipyramids by sharing their edges and corners. The title complex exhibited a 1D structure in which an alpha-gamma-type [Mo8O26](4-) anion was connected with [Cu-4(dpyh)(2)] units in a staggered manner. Under optimized conditions, complex 1 as the catalyst can achieve a highly efficient conversion (more than 99%) of thioanisole within 30 min and above 99% selectivity toward sulfoxide. Furthermore, efficient catalytic oxidation of thioether derivatives was also performed with 1 as the catalyst. In addition, the stable electrochemical sensing performance and adsorption capacity toward organic dyes were tested.