The Brook rearrangement has already become established as one of the most important molecular rearrangements in synthetic chemistry and has been applied in the generation of complexes, drug discovery, material science, and natural products synthesis. Compared to the widely known ionic mechanism, the radical Brook rearrangement is less explored because of the difficulty in generating alkoxyl radical species. This Minireview summarizes the early developments and general concept of the radical Brook rearrangement and highlights recent advances in photocatalytic reactions and transition‐metal‐catalyzed cross‐coupling reactions involving radical Brook rearrangements. We hope this survey will inspire further developments in this emerging area.

Radical chemistry has flourished as a powerful synthetic tool in organic chemistry, drug discovery and material science. Recently, the dual catalysis strategy already becomes a popular method in synthetic chemistry...