We demonstrate high efficiency and simplicity of the thiol–epoxy reaction towards preparation of a wide range of main-chain as well as end-chain multifunctional polymers.

Single and multiple post-polymerization modifications of poly(glycidyl methacrylate) scaffold through the nucleophilic ring-opening reactions of the pendent epoxide groups are described.

The thiol–epoxy ‘click’ process is employed as a polymerization reaction to prepare linear polymer chains substituted with free hydroxyl groups. Post-polymerization modification of the hydroxyl units afforded functional polymers exhibiting substituent dependent properties. In this way, functionalized macromolecules are obtained in two simple synthetic steps from commercially available monomer building blocks and reagents.