A novel organic conjugated polymer based on star‐shaped triazine‐functional triphenylamine framework poly[1,3,5‐tris(4‐diphenylamino‐phenyl)triazine] (PTDAPTz) is designed and synthesized successfully by FeCl3‐catalysted chemical oxidative polymerization. The polymer PTDAPTz powder exhibits a compactly packed pleated skirt shape‐like morphology with a high surface area (~930 m2 g−1) and a bimodal pore size distribution ranging from micropores (~0.55 nm) to small diameter mesopores (~2–6 nm). As explored as the cathode material, the obtained PTDAPTz presents the double charge–discharge process characteristics of both the free radical redox of triphenylamine unit and the bipolar redox of triazine unit in the polymer and a well‐defined multistage charge/discharge voltage plateau (~3.8 V for p‐doped and ~2.0 V for n‐doped) during the charge–discharge process. Also, the PTDAPTz demonstrates an improved capacity (stabilized at 123 mA h g−1 until 50th cycle) and the enhanced rate performance compared to polytriphenylamine (PTPAn). Specially, the discharge curve for the part of triphenylamine unit presents an obviously improved discharge plateau (~3.8 V for PTDAPTz compared to ~3.6 V for PTPAn) due to the electron‐withdrawing effect of the triazine unit to triphenylamine. The elaborate structural design and created micro‐/mesoporous morphology with the double charge–discharge process make PTDAPTz a potential candidate as the performance‐improved cathode of Li‐organic battery. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2574–2583 A novel conjugated microporous polymer based on star‐shaped triphenylamine‐triazine framework PTDAPTz was designed and synthesized simply, and the powder exhibited a pleated skirt shape‐like morphology (the sliced layer thickness of ~30 nm) with high surface area (~930 m2 g−1) and micropores of diameter of ~0.55 nm as well as mesopores of ~2–6 nm. As the cathode of an Li‐organic battery, the polymer PTDAPTz presented double charge–discharge characteristics, thus improving the voltage platform of the batteries while simultaneously guaranteeing improved capacity. [ABSTRACT FROM AUTHOR]