The activation and transformation of organic chemical bonds is a fundamental scientific problem. In the past several decades, C–S bond cleavage for the construction of C–C and C–heteroatom bonds has received tremendous attention in organic chemistry. Although significant progress has been made in the field of transition metal strategies, a variety of novel transition-metal-free strategies have also been developed using halogenated reagents, oxidants, acids, and bases. Moreover, organic photochemical and electrochemical methods have also been developed to achieve transition-metal-free C–S bond cleavage of organosulfur compounds. To date, however, no comprehensive review of transition-metal-free strategies has been reported. Therefore, we herein provide a comprehensive review of the major advances in the field of the transition-metal-free C–S bond cleavage and transformation of organosulfur compounds, including thioethers, sulfoxides, sulfones, thioacetals, sulfonium salts, and sulfur ylides.