Here we present the design and synthesis of a new robust microporous organic polymer (TPBP) decorated with phenazine groups which endowed reversibly redox-active properties. The obtained TPBP possesses relatively high surface area (359 m(2)/g) and good thermal stability. TPBP exhibits excellent catalytic capability for the oxidative homocoupling of amines with high activity and selectivity toward target products. Besides, this metal-free catalyst demonstrated excellent recyclability after 6 cycles under the investigated conditions. By means of EPR and UV-vis spectroscopy, a plausible mechanism of the amine oxidative coupling reaction was deduced via a single electron transfer from TPBP radical cations to amine substrates. (C) 2020 Elsevier Inc. All rights reserved.