Establishing chemodivergent synthetic strategies remains a daunting task in the realm of free-radical reaction manifolds. In the December issue of Chem, Glorius and co-workers resolve this challenge for selective difunctionalization of aliphatic alkenes. In the disclosed light-promoted radical relay process, switchable trifluoromethylation/alkylation or trifluoromethylation/sulfonylation of alkenes is achieved.