A practical strategy is proposed to significantly tune the spectroscopic signals and electrical properties of maleimide by chemical modification, which effectively enhances the fluorescence emission intensity and facilitates the electron charge separation of maleimide. For the first time, an easy and low-cost approach for synthesizing mono-substituted aminomaleimides by the simple heat treatment of commercially available tartaric acid and amides via a one-pot procedure has been developed. Aided by theoretical simulation, the effects of amine modification on the outstanding fluorescence properties and unique electronic character of the aminomaleimides have been deeply investigated. Furthermore, a novel aminomaleimide-based fluorescent gel-analogue with eutectic features and good conductivity has been prepared under mild conditions. The high photoelectric activity and the robust ion migration ability of the as-prepared gel-analogue, making it suitable for applications like fluorescence imaging and photovoltaics.