Herein, a visible-light-triggered photocatalyst-free radical cascade Minisci reaction of heteroarenes, alkenes, and water/alcohols to obtain diverse β-C(sp3) heteroarylated alcohols/ethers has been developed. Achieved under mild and simple conditions, this protocol is scalable and features broad substrate scope and functional group tolerance. Mechanistic studies demonstrate that the heteroarene can be served as a photocatalyst to engage single-electron transfer with persulfate.