We present a green and economical approach for the photooxidation of diverse olefins through the use of ammonium persulfate and blue light irradiation, resulting in the formation of vicinal diols from styrenes and aliphatic alkenes, and vinyl esters and diacids from α,β-unsaturated ketones. The involvement of sulfate radicals in the reaction medium was established as the primary species responsible for the selective generation of the products. A significant advantage of the method lies in its broad substrate scope and economic feasibility, making it a promising alternative to conventional transition metal photocatalysis.