Silicon carbide (β-SiC) was synthesized through an improved sol–gel method, then Ni/SiC catalysts were prepared using a hydrothermal method. The catalysts were characterized using TEM, H2- TPR, CO2- TPD and N2- TPD, etc. The results showed that the synthesized β-SiC had a large specific surface area, promoting the dispersion of Ni species and thus exposing more active sites. The interaction between Ni species and β-SiC contributed significantly to catalytic performance. Furthermore, the strong alkalinity of catalyst could adjust the bond energy of the active metal and N (M–N), which were conducive to desorption of the recombinant N2 from the metal surface, promoting to ammonia decomposition. Among the Ni/SiC catalysts, 30Ni/SiC-700 synthesized with the Ni loading of 30 wt% and calcination temperature of 700 °C, exhibited the optimal ammonia conversion rate of 93.4% at 600 °C under the space speed of 30,000 mL∙gcat −1∙h−1, and demonstrated a long-term stability, suggesting a very promising catalyst in ammonia decomposition.