The deactivation of Na 2 CO 3 , caused by the reaction between Na and Si and Al minerals in coal, is one of the key technical bottlenecks for the large-scale application of catalytic gasification. Ca can inhibit the deactivation of Na, and the binary Na−Ca catalyst shows strong synergistic effects during catalytic gasification. In this study, the deactivation behaviors of Na 2 CO 3 and the inhibition mechanism of Ca were systematically investigated by thermogravimetric, X-ray diffraction, Fourier transform infrared (FT-IR), model compounds, and FactSage thermodynamic equilibrium. The results show that the Na−Ca catalyst shows synergistic effects and more Na remains active as water-dissolved Na after gasification with Na−Ca addition. The mechanism of the inhibiting effect of Ca on Na 2 CO 3 deactivation at low temperatures (<1000 °C) is different from that at high temperatures (>1000 °C). At temperatures lower than 1000 °C, Ca inhibits the reaction between Na and Si and Al minerals; as a result, more Na remains active during catalytic gasification, which is validated by FT-IR. Meanwhile, the FactSage thermodynamic equilibrium shows that more Na 2 CO 3 exists with increasing Ca addition. With Ca/Si = 0.1, the disappearing temperature of Na 2 CO 3 is 940 °C. When Ca/Si increases to 1, the disappearing temperature of Na 2 CO 3 further increases to 1166 °C, indicating that more Na survives with Ca addition. At high temperatures (>1000 °C), Ca captures Si and a part of Na in priority to form sodium calcium silicate (Na 2 Ca 3 SiO 8 ) and calcium silicate (Ca 2 SiO 4 ). As a result, the remaining Na and Al form NaAlO 2 , which has excellent catalytic performance and contributes to the synergistically promoted catalytic performance. At low and high temperatures, Ca can act as a good deterrent to the Na deactivation.