We herein report a photoredox N-S coupling reaction between dialkyl azodicarboxylates and thiols to access sulfenamide scaffolds. This reaction proceeds under mild, green, and operationally simple conditions, offering a broad scope of sulfenamides with high yields and excellent atom efficiency. Mechanistic investigations revealed this reaction followed a photoinitiated radical pathway in which iodide plays a crucial role as both a radical initiator and a single-electron reductant.