Herein, the first example of gold-catalyzed benzylation of (hetero)aryl boronic acids with (hetero)benzyl bromides to give the corresponding cross-coupling products in moderate to good yields is reported. The reaction proceeds through a possible intermolecular SN 2-type reaction pathway to give a wide variety of di(hetero)arylmethanes as the desired products. An intriguing reaction mechanism has been proposed on the basis of control experiments, 31 P-NMR spectroscopic detection and DFT calculations.