A copper‐catalyzed approach for the N‐acylation of anilines with acetone and acetophenones via C−C bond cleavage is described. Under the developed conditions both CHCl3 and CH2Cl2 were identified as potential C1‐source to promote the transformation. The reaction features a site selective C−C bond cleavage to install the amide moieties with high functional‐group compatibility and wide substrate scope. The developed method avoids the use of sensitive and narcotic agents. The method also represents an excellent complement to the previous protocols with lower E‐factor (13.91 mg/1 mg) than current industrially used method (E‐factor 17.54 mg/1 mg). The developed approach has also been extended for the effective preparation of pyridine derivatives and paracetamol in gram scale. The course of the reaction was monitored by 1H NMR as a preliminary investigation of the reaction mechanism.