AbstractMetal‐free, visible light‐induced difunctionalizations of α‐CF3 styrenes with aryl diazonium salts and various hetero nucleophiles (ROH, H2O, N3− and F−) are described. This concise protocol provided easy access to the α‐CF3 tertiary alkyl ethers, alcohol and fluorides with good yields and excellent functional group tolerance. In addition, the four‐component “SO2” insertion reaction also worked efficiently to produce the α‐CF3, β‐sulfonyl ethers in moderate to good yields. A radical‐polar crossover coupling pathway was proposed for the C−O bond formation.