Electrochemically active polyluminol was synthesized using an oxidative chemical polymerization reaction. The chemically polymerized luminol (CpLum) exhibited reversible oxidation and reduction reactions with fast kinetics. From Fourier transform infrared spectroscopy analyses, the polymerization occurred by the conversion of primary amine groups into secondary amine groups. The polymer contained benzoid and quinoid segments which were confirmed by UV–visible spectroscopy and X-ray photoelectron spectroscopy. Thermal analysis revealed the semi-crystalline nature of CpLum, with two thermal events at 99°C and 152°C corresponding to a glass transition and a melting temperature. The interesting features and electrochemical activities may lead to applications in energy storage.