A simple and efficient method for the regioselective thiolation of p-quinone methides with sodium aryl/alkyl sulfinates has been established using an acid/phosphine-induced radical route under transition-metal-free conditions. A broad range of sodium aryl/alkyl sulfinates and p-quinone methides (p-QMs) are compatible for the reaction, giving the expected products with good to excellent yields. Control experiments were also performed to gain insights into the generation mechanism of thiyl radicals and hydrogen-atom transfer process. This protocol provides a safe and feasible way for the formation of carbon-sulfur bonds.