A Sn-based porphyrin polymer (TAPP(Sn)-FAC) synthesized in a mild condition was introduced for the Hg0 removal in flue gas. The properties characterization of materials revealed the two-dimensional sheet structure, an amorphous structure and high stability of TAPP(Sn)-FAC, and Sn was successfully incorporated into TAPP-FAC in the form of SnN. The removal performance of Hg0 under different conditions was investigated using a lab-scale fixed-bed reactor. TAPP(Sn)-FAC presented an excellent Hg0 removal efficiency from 100 °C to 250 °C, which can reach 8 mg/g of Hg0 capture capacity at 100 °C for 300 min. Besides, TAPP(Sn)-FAC had a strong sulfur and water resistance, and the presence of NO and O2 had a facilitating effect for Hg0 removal. Moreover, the existence of Sn can enhance the Hg0 adsorption and oxidation capacity of TAPP(Sn)-FAC by promoting the electron transfer process. Furthermore, TAPP(Sn)-FAC presented an excellent chemical stability, which was a promising material in the Hg0 removal in flue gas.