Four kinds of main-chain benzoxazine polymers (PBZ) containing triarylamine (TAA) units were synthesized by Mannich reaction and characterized by H nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR) techniques, etc. Thermal, optical, photophysical and electrochemical properties were studied. The 50% of char residue is left in N at 800 °C. The polymers are soluble in common organic solvents and easily spin-coated onto indium‑tin oxide (ITO) coated glass substrates. All the polymers have voltage window ranging from 0 to 1.8 V, and the colors change from yellowish to dark red when voltage is applied. Meanwhile, device assembled from polymer exhibit significant color changes. Furthermore, the polymers also have promising potential application in explosive detection and resistance memory devices.