Abstract2‐Chloro and 2‐phenoxy substituted 1,1‐bis(diethylamino)ethylenes (4aand4c) react with elemental sulfur at room temperature to give the inner salt, bis(diethylamino)carbeniumdithiocarboxylate (1a), in excellent yields with extrusion of hydrogen chloride and phenol, respectively, thus providing a new and convenient synthesis of the structurally interesting inner salt. X‐ray single crystal structure analysis of1areveals that the NCN and SCS planes are nearly vertical to each other with a dihedral angle of 82.0° and that the positive and negative charges are delocalized over the NCN and SCS moieties, respectively. Results of solid‐state13C NMR of1a