Mixed‐condensation reaction of 1,8‐naphthalenedicarbonitrile and a 4,5‐disubstituted phthalonitrile provided a series of phthalocyanine (Pc) analogues with azaphenalene (AP) moieties in place of the isoindole moieties. Monosubstituted species, APPc, and the two structural isomers of disubstituted species, adj‐AP2Pc and opp‐AP2Pc, were successfully isolated by gel‐permeation chromatography on HPLC apparatus. Their structures were elucidated by 1H NMR spectroscopy and X‐ray crystallographic analysis. Replacement of the isoindole moieties with azaphenalene moieties created six‐membered‐ring units in the core and caused distortion of the molecular structures. The Q‐band absorption shifted to the red upon an increase in the number of azaphenalene units; the shape of the absorption spectra depended on the molecular symmetries. APPc and opp‐AP2Pc showed a large splitting of the Q band, whereas adj‐AP2Pc exhibited a single broad Q band. These changes in the absorption spectra, as well as the unique electronic structures, are discussed in detail, based on magnetic circular dichroism spectra, electrochemical measurements, and density functional theory calculations.