We have developed a novel protocol for carbonylative homocoupling of arylboronic acids using dithiocarbamate esters as the carbonyl alternative. A series of arylboronic acids underwent smooth reaction with dithiocarbamate ester (Me2NCS2Me) in the presence of Pd(PPh3)2Cl2 catalyst, Cu(OAc)2·H2O additive, and Na2CO3 in DCE solvent, producing the biaryl ketones efficiently. The mechanism has been studied with the help of several control experiments that reveal the probability of thioamide intermediacy. Chemoselective homocoupling allows the postsynthetic modification of the product.