A method for direct, auxiliary-assisted alkoxylation and phenoxylation of β-sp<sup>2</sup> C–H bonds of benzoic acid derivatives and γ-sp<sup>2</sup> C–H bonds of amine derivatives is reported. The reaction employs (CuOH)<sub>2</sub>CO<sub>3</sub> catalyst, air as an oxidant, phenol or alcohol coupling partner, DMF, pyridine, or DMPU solvent, and K<sub>2</sub>CO<sub>3</sub>, tetramethylguanidine, or K<sub>3</sub>PO<sub>4</sub> base at 70–130 °C