A highly-efficient and practical method for S-alkylation of arylthioureas was reported. Using tetraalkylammonium salts as alkylation reagents, a series of 68 S-substituted aryl-isothioureas were obtained in good to excellent yields under transition-metal-free conditions. The protocol features simple performance, broad functional group tolerance, good to excellent yields, and easily available starting materials, showing potential synthetic value for the preparation of diverse biologically or pharmaceutically active compounds.