To synthesize a crystalline polymer is unconventional. Here, we found the well-defined hexagonal or rectangular cubical shape of poly(aniline-co-2-nitroaniline)s PA-co-2-NAs through scanning electron microscopy. Enhanced crystallinity of PA-co-2-NAs has been confirmed by differential scanning calorimetry and particle size analysis. The edge and structural morphology of the material has been studied by SEM and TEM analysis. The physical nature of -NO(2)groups and the bandgap between HOMO and LUMO of the copolymer have been evaluated by FTIR and UV-vis spectroscopy, respectively. The overall reduced particle size of A-co-2-NA supports the improved percentage of the crystallinity of the material. The spatial resolutions at nano-level examined through (TEM) also confirm the sharp edges of the material. The diminished electrical conductivity of the copolymer is determined by applying the four-probe method. [GRAPHICS] .