A new strategy was developed for activation of C–N bond via formation of an amine–I₂ charge-transfer complex, which facilitates the inert C–N bond activation via oxidative addition with Ni(0). This strategy has been successfully applied in the Ni-catalyzed carbonylation of benzylamines via direct insertion of CO into the C–N bond, which provided a straightforward and rapid approach to arylacetamides in the presence of catalytic amounts of I₂ and Ni catalyst. Mechanistic studies suggested that a benzyl radical generated via the oxidative addition was involved in the present reaction.