A green and mild palladium-catalyzed solvent-free α-arylation reaction of ketones was disclosed for the first time. Using the robust N -heterocyclic carbene–palladium complex (SIPr) Ph2 Pd(cin)Cl, (hetero)aryl chlorides and ketones were able to generate monoarylation products in excellent yields under solvent-free conditions, with a total of 41 examples. Furthermore, the protocol has been demonstrated to be suitable for multigram-scale preparation with a high yield.