Nickel(II) and copper(II) complexes of redox-switchable 20π, 19π, and 18π 5,15-dialkyl-10,20-diaryl-5,15-diazaporphyrins were prepared through a metal-templated cyclization method. Furthermore, the terminal silyloxy groups in the peripheral N-alkyl chains were transformed into hydroxy groups by deprotection. It is worth noting that redox reactions between the 19π and 18π systems bearing hydroxy groups caused a change in the water solubility of the diazaporphyrin chromophore.