The merits of thiol-click chemistry and its potential for making new forays into chemical synthesis and materials applications are described. Since thiols react to high yields under benign conditions with a vast range of chemical species, their utility extends to a large number of applications in the chemical, biological, physical, materials and engineering fields. This critical review provides insight into emerging venues for application as well as new mechanistic understanding of this exceptional chemistry in its many forms (81 references).

This review highlights examples of recent applications of both the radical-mediated and base/nucleophile-initiated thiol-ene reactions in polymer and materials synthesis. Initial discussion focuses on mechanistic aspects of these reactions and also notes some of the structural considerations, with respect to reactants, that should be considered when practising such chemistries. The review is not intended to be exhaustive but rather to serve as an illustration of the impressive versatility and clear potential of these thiol-based “click” reactions and to highlight examples demonstrating its broad utility.

This contribution serves as an update to a previous review (Polym. Chem. 2010, 1, 17–36) and highlights recent applications of thiol–ene ‘click’ chemistry as an efficient tool for both polymer/materials synthesis as well as modification. This current contribution covers examples from the literature published up to ca. mid 2013. It is not intended to be exhaustive but rather serves to highlight many of the new and exciting applications where researchers have applied thiol–ene chemistry in advanced macromolecular engineering and materials chemistry.