A novel method for Pd-catalyzed triflination of aryl and heteroaryl triflates using NaSO<sub>2sub>CF<sub>3sub> as the nucleophile is described. The combination of Pd<sub>2sub>(dba)<sub>3sub> and RockPhos formed the most effective catalyst. A broad range of functional groups and heteroaromatic compounds were tolerated under the neutral reaction conditions. The order of reactivity ArOTf ≥ ArCl ≥ ArBr is consistent with transmetalation being a slow step of the reaction.