Abstractperi‐Annulation of naphthalane, an important tool for realization of wide range of functional materials, is presently accomplished with limited few functional groups like imide, amide and diamine‐derivative (perimidine). To increase the diversity, we have incorporated α‐keto aldonitrone as a new functional group, and herein report about five peri‐naphthoisatogens (PNTIs) dyes. The synthesis were accomplished using an unusual reaction of aromatic nitro group, which is nucleophilic attack of a C‐nucleophile (enol) to the N‐atom of nitro group. In five different 5‐alkylamino‐8‐nitro‐1‐acetylnaphthalenes, intramolecular acid‐catalyzed nucleophilic attack of enol moiety to the N‐atom of nitro group produced α‐keto aldonitrone via addition‐elimination mechanism. The PNTIs showed characteristics of 1,3‐dipole and reacted with ethyl acrylate to produce isoxazolidine ring, which subsequently converted into aza phenalenone derivative via ring cleavage. Both the PNTI and the corresponding derivative strongly absorb in the visible region, displaying absorption maximum at 551 and 561 nm (in CHCl3) respectively. Compared to the popular analogous dye naphthalene monoimides, PNTIs showed bathochromic shift of absorption maximum by more than 100 nm. The emission maximum for the PNTI and its derivative in chloroform were observed at 594 and 635 nm respectively.