The organic ligand (1‐methyl‐1H‐benzo[d]imidazol‐2‐yl)methanol (HL1) was used to react with Cu(ClO4)2·6H2O and triethylamine at 80°C to afford the complex [Cu4(L1)6]·(ClO4)2·CH3CN (1). Every four‐coordinated Cu(II) ion is surrounded with NO3 coordinated environment, and every five‐coordinated Cu(II) ion is surrounded with N2O3 coordinated environment. Changing the metal salt to Zn(NO3)2·6H2O, and after adding CH3COONa, afforded the complex [Zn4(L1)4(NO3)2(CH3COO)2] (2), in which every five‐coordinated Zn(II) ion is surrounded with NO4 coordinated environment. High‐resolution electrospray ionization mass spectrometry results revealed that complex 1 broke into the most stable fragment [Cu2(L1)3]+, and it also can assemble high nuclear peaks in solution. For complex 2, it was found that the complex exhibited different component distribution in solution. Not only were there substitutions between coordinated anions, but the high nuclear peaks could also be detected.