Oximinoalkylamines were found to be efficient ligands for acceleration of the CuAAC reaction. ‘Mixed’ oxime–triazole ligands Tz尾Ox2 and Tz2尾Ox demonstrate an approximately 10-fold enhanced acceleration effect compared to commonly employed ligand TBTA using 0.1xA0;mol % of the [Cu]/L catalytic system. The optimal catalytic system based on readily available Tz尾Ox2 provided 1,4-disubstituted triazoles in high yields with short reaction times.