Abstract A novel oxidative coupling of acetophenones with N,N‐dimethylformamide to synthesize aryl‐α‐ketoamides was developed by using copper oxide and iodine as the additives. For this conversion, DMF works not only as the solvent but also as the surrogate of dimethylamine. Besides, additional oxidants, such as peroxides or dioxygen, are not necessary, and atmospheric oxygen acts as the oxidant.