By intentionally involving in situ ligand transformation in the reaction system, two inorganic-organic hybrid polyoxovanadates (POVs), [Co(HDTBA)V2O6] (1) and [Ni(H2O)(2)(DTBA)(2)V2O4(OH)(2)]center dot 4H(2)O (2), have been synthesized by using a hydrothermal method, where the 3,5-di[1,2,4]triazol-1-ylbenzoic acid (HDTBA) ligand originated from in situ hydrolysis of 3,5-di[1,2,4]triazol-1-ylbenzonitrile in the self-assembly process. The inorganic layers [Co-2(V4O12)](n) containing [V4O12](4-) circle clusters were linked by HDTBA ligands to yield a 3D framework structure of compound 1. There existed a kind of binuclear [(DTBA)(2)V2O4(OH)(2)](2-) vanadium cluster grafted directly by two DTBA ligands through the sharing of carboxyl oxygen atoms in compound 2, further extended into a 2D layer by nickel centers. The investigations on the catalytic properties indicated that compounds 1 and 2 as heterogeneous catalysts, especially 2, owned satisfying catalytic performances for catalyzing the selective oxidation of sulfides to sulfoxides in the presence of tert-butyl hydroperoxide as an oxidant, accompanied by excellent conversion of 100% and selectivity of above 99%, providing a promising way for developing inorganic-organic hybrid POVs as effective heterogeneous catalysts for catalyzing the selective oxidation of sulfides.