With the growing emphasis on green synthesis, mechanochemistry has garnered significant interest from researchers, owing to its characteristics, including solvent-free environment, low energy consumption, and environmental sustainability. Notably, mechanochemically driven radical reactions benefit from the unique reaction environment offered by ball milling, enabling access to intermediates and products that are challenging or even unattainable under conventional solution-phase conditions. Consequently, such reactions have demonstrated considerable potential in the realm of organic synthesis. Herein, the progress of radical reactions performed under mechanochemical ball-milling conditi、ons over the past decade is systematically reviewed. Based on the difference of radical initiation mechanisms, these reactions are categorised into three types: (1) single-electron transfer (SET) processes mediated by piezoelectric materials activated by mechanical force, (2) mechanically induced homolytic bond cleavage, and (3) metal-regulated radical processes promoted by mechanical force. Representative examples are selected to illustrate the core features and application scopes of each mechanistic pathway. Finally, the potential applications and future development trends of mechanochemically driven radical reactions are also discussed.

Key words: mechanochemistry, free radicals, piezocatalysis, homolytic scission, metal regulation, green synthesis