In spite of significant advances in redox-active porphyrin-based materials and catalysts, little attention has been paid to 20π and 19 π porphyrins because of their instability in air. Here we report the meso-modification of 5,10,15,20-tetraarylporphyrin with two nitrogen atoms, which led to redox-switchable 20π, 19π, and 18π 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (TADAPs). Three kinds of metal(II) complexes and free bases of TADAP were prepared by the metal-templated annulation of the corresponding metal-bis(dipyrrin) complexes. The inductive and resonance effects of the meso-nitrogen atoms on the aromatic, optical, electrochemical, and magnetic properties of the entire TADAP π-systems were assessed by using various spectroscopic measurements and density functional theory calculations. The aromaticity and π–π* electronic transition energies of the TADAPs varied considerably, and were shown to be dependent on the oxidation states of the π-systems. In contrast to the isoelectronic 5,10,15,20-tetraarylporphyrin derivatives, the 20π and 19π TADAPs were chemically stable under air. In particular, the 19π TADAP radical cations were extremely stable towards dioxygen, moisture, and silica gel. This reflected the low-lying singly occupied molecular orbitals of their π-systems and the efficient delocalization of their unshared electron spin. The capability of MgTADAP to catalyze aerobic biaryl formation from aryl Grignard reagents was demonstrated, which presumably involved a 19π/20π redox cycle.