Acetophenone and deoxybenzoin derivatives are selectively α‐arylated using a combination of very small amounts of palladium acetate and diphenylphosphine oxide as catalyst system and water as the only solvent. Target di‐ and triarylethanones are isolated virtually free of metal residues, and the reaction is amenable to gram‐scale. A mechanistic proposal based on TEM images, poisoning experiments, kinetic plot and ESI‐MS spectrometry is also provided.magnified image