An efficient iodine‐mediated construction of S−N bond was developed. Such a cross‐dehydrogenative coupling of heterocyclic thiols with amines proceeded smoothly under metal‐free and base‐free conditions, and afforded a series of sulfenamides in good to excellent yields. The easily available substrates and convenient synthetic procedure illustrate potential synthetic value of this protocol for the preparation of sulfenamide related biologically or pharmaceutically active compounds. An iodine‐mediated sulfenamides synthesis was reported. By using iodine as oxidant, various heterocyclic thiols and amines (mainly secondary amines) could smoothly proceed the CDC reaction, affording the target N−S formation products with good yields. The protocol features metal‐free, easy performance, and short reaction time.