Chrysoidine (CHRY) is a type of azo‐dye extensively used in industry. This study delineates 2 routes as enzymatically and oxidatively polycondensation of chrysoidine for the syntheses of poly (chry‐enz) and poly (chry‐ox), respectively. The molecular structures of enzymatically and oxidatively polymerized chrysoidine were described by the FT‐IR, UV‐Vis, 1H‐NMR, and 13C‐NMR techniques. The molecular structures were obtained to be different as in the cyclization process of the enzymatic polymerization. Solvatochromic behavior in selected polar solvents on the optical properties of poly (chry‐ox) were studied. Further characterization was implemented by fluorescence (PL), electrochemical, thermogravimetric (TG‐DTA), cyclic voltammetry (CV), and differential scanning calorimetry (DSC) measurements. The number of average molecular weight of poly(chry‐ox) was found to be higher than that of poly(chry‐enz). Photoluminescence (PL) measurements enlightened the response of poly (chry‐ox) with intense light emissions upon a bicolor irradiation by Ultra‐Violet and visible light. CV technique was utilized to make a comment about HOMO‐LUMO energy levels and electrochemical (
Eg') band gaps of the polymers. Optical and electrochemical band gaps of poly (chry‐enz) were lower than those of poly (chry‐ox), proving the successful synthesis of π‐conjugated structure of poly (chry‐enz). To further make comments about the features of the polymers, scanning electron microscopy (SEM) images were exemplified to study the surface forms of the polymers. Surface morphology of poly (chry‐enz) was seen as agglomerates of grains toward the out‐of‐plane direction. As the polymerization method was changed, the morphology was transformed into a flat‐smooth surface present with visible holes for poly (chry‐ox).