We herein report the preparation and characterization of a new type of fully aromatic polyazomethines (PAMs) with the cyano functional group. For synthesizing this compound, two homopolymers, poly(nitrilo-2-cyano-1,4-phenylenenitrilomethine- 1,3-phenylenemethine) (mPAM) and poly(nitrilo-2-cyano-1,4-phenylenenitrilomethine- 1,4-phenylenemethine) (pPAM) and their copolymers, poly[(nitrilo-2-cyano-1,4- phenylenenitrilomethine-1,4-phenylenemethine)-co-(nitrilo-2-cyano-1,4-phenylenenitrilomethine- 1,3-phenylenemethine)]s (coPAMs), were synthesized via the polycondensation of terephthalaldehyde (TPA), isophthalaldehyde (IPA), and 2-cyano-1,4-phenylenediamine (cyPPD) monomers in an NMP/CaCl₂ solvent system. The ¹H-NMR and FT-IR spectra confirmed that all the aromatic PAMs were successfully synthesized and that the output compositions of coPAMs were almost identical to the relative input composition of TPA and IPA to cyPPD. mPAM, with a nonlinear meta-phenylene moiety, exhibited good solubility in organic solvents such as NMP, DMSO, and DMAc, while pPAM and coPAMs were partially soluble in those solvents owing to the rigid para-phenylene moiety in the main chains. Accordingly, unlike mPAM, pPAM and coPAMs were semicrystalline, as revealed by their Xray diffraction patterns. Interestingly, the peak decomposition temperatures (667-769 °C) in air were higher than those (452-594 °C) in nitrogen, although the residues (74-81%) at 800 °C in nitrogen were far higher than those (16-47%) in air.