Sulfur-containing compounds, abundant in various natural products, have potential applications in pharmaceutical, agricultural, and chemical synthesis . Among the organosulfur compounds, the derivatives with unique SS bonds are particularly important due to their vast applications; the family includes: disulfides, 7,8 thiosulfinates 9,10 and thiosulfonates. In this regard, the protocols that install a new SS bond is synthetically very important. Among SS bond containing molecules, thiosulfonates -also known as the S-esters of thiosulfonic acid and sulfonothioates-are a special class, where one of the sulfur of the SS bond is a dioxide, i.e., SO2, and the other one is a simple sulfide. While the oxidation state of the S-atom in the former is S(VI), the latter has S(II). This polar nature of the asymmetric SS bond makes the thiosulfonates amphiphilic, where one sulfur atom is electrophilic and the other is nucleophilic. Thus, thiosulfonates can serve as sulfenylating as well as sulfonylating reagents in polar/ionic reactions. Furthermore, homolytic cleavage of the SS bond produces sulfonyl and sulfenyl radicals, which are synthetically very useful. The above discussion clearly projects thiosulfonates as an efficient sulfonylating reagent, which are considered better compared to disulfides. Furthermore, when compared with sulfonyl halides, these sulfonylation reagents are more stable and easy to handle. Thiosulfonates are also employed as sulfenylation reagents, for example, CS bonds were installed when treated with compounds bearing active methylene groups. Apart from synthetic uses, thiosulfonates found to exhibit medicinal properties like antimicrobial, antibacterial, antiviral, antifungal, etc., as well as employed for antiplatelet therapy. A number of methodologies have thus far been reported to access thiosulfonates. Four main strategies followed for their synthesis are: i) from thiols or disulfides in the presence of oxidants with or without involvement of transition metals, ii) the addition of disulfides or thiols to sodium sulfonate, iii) the reductive coupling of sulfonyl chlorides and sulfonyl hydrazides with or without metal catalyst, and iv) the reaction of sulfonyl halides with other thiols or thiolates. In addition, electrochemical methods are also known for the synthesis of thiosulfonates. Despite the availability of several reagents for the synthesis of thiosulfonates in the literature, only a few are applicable for one-pot direct oxidation of thiols to thiosulfonates. Most of these methodologies suffer from several drawbacks such as complicated procedures for the synthesis of reagents, the need to activate reagents, use of hazardous chemicals, and expensive techniques. Thus, general and facile protocols for direct oxidative transformation of thiols to thiosulfonates remain much sought after.