In the presence of new air-stable triarylphosphine 2, palladium-catalyzed Suzuki reactions of a wide array of aryl chlorides can be accomplished in uniformly good yield, including couplings of very sterically demanding and electronically deactivated substrates; activated aryl chlorides can be coupled at room temperature. In terms of scope and mildness, Pd-2 compares well with other catalyst systems that have been described for Suzuki reactions of aryl chlorides, thereby establishing that triarylphosphines should be regarded as fertile ground for future ligand-design efforts for palladium-catalyzed couplings of aryl chlorides.