Herein, CoN4, CuN4, and NiN4 complexes with a 14-membered ring hexaazamacrocycle ligand H2HAM were synthesised as precursors for ORR and CO2RR catalysts via a one-pot, gram-scale synthesis procedure, which involved microwave heating for only 10 min. Detailed structures of the obtained 14MR-MN4 complex were revealed by single-crystal X-ray diffraction measurements.