Main observation and conclusionrnThe development of bifunctional catalysts has drawn much attention in realizing efficient and feasible catalytic systems to meet the diverse demand of potential industrial applications.Design of stable and powerful bifunctional catalysts for various catalysis systems is highly desirable yet largely unmet.Here,three kinds of decavanadate-based transition metal hybrids (DTMH) (i.e.,Co-DTMH,Ni-DTMH and Ag-DTMH) have been successfully synthesized through a pH tuning strategy and further characterized.Specifically,the rare MOsN six-coordinated transition metal coordination modes have been detected in Co-DTMH and Ni-DTMH,while Ag atoms in Ag-DTMH exhibited three-and five-coordinated geometries with the tuning of specially selected imidazole ligands.Thus-obtained clusters can serve as powerful bifunctional catalysts for both sulfide oxidation and C-C bond construction.Remarkably,Ag-DTMH demonstrated excellent heterogeneous bifunctional catalytic properties in the selective oxidation of sulfides and construction of C-C bond (yields up to 99％),which enable successful recycling for three cycles with remained catalytic activities and structure stability.The newly designed decavanadate-based transition metal hybrids with bifunctional property hold high promise in the practical applications like continuous catalysis or flow bed reactions.