Aryl/vinyl thioethers containing C(sp 2)-S bonds are prevalent in biologically relevant molecules and compounds with other potential applications. Around the past decade, rapid progress has taken place in the research area of C(sp 2)-S construction, and a large number of efficient new catalytic systems as well as structurally versatile substrates have been identified for such reactions, which significantly enriched the content of the synthetic methodologies on C(sp 2)-S bond formation. This review introduces mainly the research advances on transition metal-free C(sp 2)-S bond forming reaction by means of C(sp 2)-H bond functionalization over the period of 2001~2016. Keywords transition metal-free; C(sp 2)-H bond; (Hetero)aryl; vinyl; C(sp 2)-S bond formation
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