A series of aromatic electroactive polyimides bearing p-phenoxy pendant at main chain were synthesized as fluorescent materials. The PIs were prepared from electroactive diamine N-1-(4-aminophenyl)-N-1-(4-phenoxyphenyl)benzene-1,4-diamine. The structure of the polyimides was characterized by the fourier transform infrared spectroscopy, Carbon, Hydrogen and Nitrogen analyses, and gel permeation chromatography. The polyimides were analyzed for their photophysical and electrochemical properties by ultraviolet-vis spectral analysis photoluminescence spectroscopy and cyclic voltammetry. Thermal stability of the polyimides was evaluated by thermogravimetric analysis and differential scanning calorimetry. The observed behavior of our synthesized polyimides revealed their shallow highest occupied molecular orbital levels, low E-g, blue light emission and stable redox behavior, and good thermal and mechanical stability making our synthesized polyimides useful for future optoelectronics. [GRAPHICS] .