An efficient palladium-catalyzed electrooxidation C–H acylation reaction of N -nitrosoanilines with α -oxocarboxylic acids was developed. The anodic oxidation of the Pd(II) intermediate was found to be the key to complete the reaction. In this case, the N -nitroso group was observed to be an effective directing group for C–H activation reaction. Moreover, the synthetic transformation of derivatives of natural products (L-menthol, dehydroepiandrosterone, and pregnenolone) was successfully realized. Finally, flow electrochemical synthesis of some substrates was achieved. An efficient palladium-catalyzed electrooxidation C–H acylation reaction of N -nitrosoanilines with α -oxocarboxylic acids was developed.