A controllable and rapid synthesis of disulfides and thiosulfonates from sodium sulfinates mediated by hydroiodic acid is presented for the first time. In these reactions, ethanol and H2O are employed as solvents to generate different products, thiosulfonates can be further transformed to corresponding disulfides in an ethanol reaction system. Moreover, these simple methods are environmentally benign and can be performed under mild conditions with a short reaction time, showing good functional group tolerance.