<p indent="0mm">Alkene difunctionalization supplies a robust tool for the conversion of simple alkenes to complex molecules by simultaneously installing two different functional groups to alkenes. In particular, radical-mediated difunctionalization of alkenes has received extensive attention from synthetic chemists, because of the inherent features of mild reaction conditions and high product diversity. By taking advantage of designed bifunctional reagents, in which a radical donor and a migrating group are tethered by a linker, the docking-migration process proceeding through consecutive radical addition to alkene and intramolecular functional group migration provides an efficient strategy for alkene difunctionalization. The approach demonstrates broad scope of alkene substrates that activated and unactivated alkenes as well as complex alkenes are suitable substrates. This account summarizes the progress from our group in alkene difunctionalization relying on the docking-migration strategy.