1,2‐Dithio‐1‐alkenes are biologically active compounds widely implemented throughout organic synthesis, functional materials, coordination chemistry, and pharmaceuticals. Traditional methods for accessing 1,2‐dithio‐1‐alkenes often demand transition metal catalysts, specialized or air‐sensitive ligands, high temperatures, and disulfides (R2S2). Herein, a general and efficient strategy utilizing ethynylbenziodoxolone (EBX) reagents and thiols is presented that results in the formation of 1,2‐dithio‐1‐alkenes with excellent regioselectivity and stereoselectivity through unprecedented reactivity between the EBX and the thiol. This operationally simple procedure utilizes mild conditions, which result in a broad substrate scope and high functional‐group tolerance. The observed unexpected reactivity has been rationalized through both experimental results and DFT calculations. Uniquely reactive: Ethynylbenziodoxolone (EBX) reagents react with thiols to form 1,2‐dithio‐1‐alkenes with cis regiocontrol. Experimental results and DFT calculations showed that the cis regioselectivity observed in the final products is due to cis‐selective nucleophilic RSH addition followed by cis‐specific radical RSH addition. This process is unique to EBX reagents.