The study deals with the vulcanization of carboxylated nitrile butadiene rubber (XNBR) having synergistic combinations of accelerators comprising thiophosphoryl disulfide as one of the components. Other constituent accelerators employed in the present investigation are 2-mercaptobenzothiazole (MET), 2-mercaptobenzothiazyl disulfide (MBTS), bis(N-oxydiethylene)disulfide (ODDS), N-oxydiethylene 2-benzothiazole sulfenamide (OBTS), etc. The binary combinations of thiophosphoryl disulfides with OBTS exhibited the highest mutual activity in the respective areas, so far as the physical properties are concerned. Structural characterization of different thiophosphoryl disulfide-accelerated XNBR vulcanizates, including those formed from the synergistic combinations with OBTS, were studied using a methyl iodide probe. It was found that the amount of sulfidic crosslinks arising from the reaction between - COOH groups of XNBR and thiophosphoryl disulfides, actually controls the network structure as well as the physical properties of the vulcanizates.