A visible-light-promoted direct thiolation of α-C(sp³)–H in ethers with thiosulfonates was developed for the preparation of α-arylthioethers using easily availably Na₂-eosin Y and TBHP as a photocatalyst and oxidant. This reaction occurred smoothly under the irradiation of 5 W blue light at room temperature and generated the corresponding products in good to excellent yields.