Hemiporphyrazines are a large family of phthalocyanine analogues in which two isoindoline units are replaced by other rings. Here we report unambiguous identification of 20 pi-electron structure of triazolehemiporphyrazines (1, 2) and thiazolehemiporphyrazine (3) by means of X-ray analysis, various spectroscopic methods, and density functional theory (DFT) calculations. The hemiporphyrazines were compared in detail with dibenzotetraazaporphyrin (4), a structurally related 18 pi-electron molecule. X-ray analysis revealed that tetrakis(2,6-dimethylphenyloxy)-triazolehemiporphyrazine (1b) adopted planar geometry in the solid state. A weak absorption band with a pronounced vibronic progression, observed for all the hemiporphyrazines, was attributed to the lowest pi-pi* transition with the electric-dipole-forbidden nature. In the case of intrinsically chiral vanadyl triazolehemiporphyrazine (2), a large dissymmetry (g) factor was detected for the CD signal corresponding to the lowest pi-pi* transition with the magnetic-dipole-allowed nature. Molecular orbital analysis and NICS calculations showed that the azolehemiporphyrazines have a 20 pi-electron system with a weak paratropic ring current.