2-Mercaptobenzothiazole has found widespread industrial applications for the vulcanisation of rubber and, more recently, as a key component of the modified Julia olefination reaction. This review surveys the chemistry of 2-mercaptobenzothiazole, including its aromatic substitution reactions, redox chemistry and factors governing the regioselectivity of its alkylation reactions. In addition, the emerging synthetic uses of this heterocycle, including its application to the deoxygenation of epoxides, and the preparation of alkynes, are described.