The invention discloses a novel aza-condensed ring compound, its preparation method and application. The present invention has synthesized a novel aza-condensed ring compound through a very simple method, and its general chemical structure is shown in formulas (IX), (X), and (XI), wherein AR is the number of benzene rings ≥0 condensed rings, benzene ring azaheterocycles, fused ring benzazene heterocycles, benzene rings connected to halobase azaheterocycles or condensed rings connected to halobase azaheterocycles, R is ≥ 12 carbon atoms straight-chain or branched-chain alkyl groups. The synthesis method of the invention is simple and convenient, and the compound has good solubility. Compared with other acene structures, the method synthesizes a series of acene analogues with fewer steps and higher yield. The series of products synthesized by this simple method can obtain a structure with an effective conjugate length of more than sixteen rings, which is extremely conducive to the transmission of electrons, and the maximum absorption wavelength is in the visible light field. The battery (OPV) field has potential application prospects.