Calix[4]-crown-5-sulfonyl cyclothiourea derivatives 6 and 7 were synthesized from calix[4]-crown-5-monosulfonylethylene-diamine derivatives 4 and 5 and carbon disulfide through nucleophilic addition and subsequent cyclization of intramolecule at room temperature in aqueous solution. The advantages of the novel protocol are the mild reaction condition, free organic solvent, simple final treatment, easy isolation of products and excellent yields.