AbstractAdvances in controlled radical polymerization (CRP) have facilitated access to well‐defined polymers with controlled molecular weight, topology, and functionality. However, despite the benefits afforded by many CRP techniques, control over these key polymer attributes often comes at the expense of polymerization rate. One method proposed for accelerating chemical synthesis is microwave heating. This review highlights recent examples of microwave heating being applied during reversible addition‐fragmentation chain transfer (RAFT) polymerization. In addition to successfully leading to homopolymers from a variety of monomers, block copolymers have also been prepared by microwave‐assisted RAFT, which suggests that the high polymerization rates observed do not necessarily lead to significant end group loss from termination. Despite significant debate regarding the origin of rate enhancement observed during microwave‐assisted reactions, the reports included herein provide insight into mechanisms by which well‐defined functional polymers can be prepared in an accelerated fashion.