In this study, we have discovered the versatility of the dithiosulfonate reagent (ArSO2-SSR) in transition metal catalyzed selective hydrodisulfuration of unactivated alkenes. The hydrodisulfuration displays a unique Markovnikov selectivity with a Salen-cobalt complex, while an anti-Markovnikov selectivity is observed when employing a nickel/bidentate N-donor ligand. Furthermore, precise control over nickel/ligand enables the successful achievement of remote site-selective hydrodisulfuration for both internal and terminal alkenes via a chain-walking process. In these processes, silanes are employed as a hydride source. Mechanistic insights into these innovative catalytic systems are also elucidated. Experimental findings suggest that Markovnikov hydrodisulfuration is likely to proceed through radical substitution on dithiosulfonate reagents, while nickel-catalyzed anti-Markovnikov selectivity and remote site-selectivity likely occur via the radical addition of the reductively formed dithiosulfonate radical anion ([ArSO2-SSR]·¯) to alkyl Ni(II) species (alkyl-Ni(II)LnX) and subsequent reductive elimination on Ni(III) intermediate (alkyl-Ni(III)Ln(X)-SSR) as the key steps based on DFT calculation analysis.