Sulfur-containing compounds exhibit potent significance in drug molecules. Thiosulfonates as 1,3-thiosulfonylation reactants to olefins have yet to be investigated. Herein, we report photoinduced 1,3-difunctionalization of β,γunsaturated ketones with thiosulfonates, which undergo a radical 1,2-acyl shift. The protocol features mild conditions, high regioselectivity, and 100% atom economy.