Abstract The first 100% atom-efficient and odorless protocol for carbon–sulfur bond formation in a deep eutectic solvent (DES) as both the reaction medium and catalyst is reported. The biodegradable and inexpensive DES provides an efficient and convenient ionic reaction medium for the thia-Michael addition with in situ generation of S- alkylisothiouronium salts in place of thiols without the urea by-product segment. This ...