The present review covers basic work on the synthesis, chemical reactions and practical application of organic thiosulfonates published before 1969, and gives more detailed attention to papers which appeared in the literature during the last 20 years. Three approaches to the synthesis of thiosulfonates, namely, (i) oxidation-reduction techniques, (ii) nucleophilic and, (iii) electrophilic introduction of an RSO2S moiety into an organic substrate, are presented in this review. (The synthetic part is divided into two subchapters: the synthesis of “symmetric” thiosulfonates and of “unsymmetric” ones). Nucleophilic substitution, electrophilic reactions, thermolysis and photolysis of thiosulfonates are also described. A special chapter serves as a brief summary of some practical applications of thiosulfonates.