Mo2C/γ-Al2O3 (MCAS) and Ni modified Ni-Mo2C/γ-Al2O3 (MNCAS) catalysts were prepared via co-impregnation and temperature-programmed carbonization using γ-Al2O3 doped Y molecular sieve as carrier, ammonium heptadolybdate (AMT) and hexamethylenetetramine (HMT) as raw materials, and NiCO3•2Ni(OH)2•4H2O as modifying agent. The synthesized catalysts were characterized by XRD, ICP, N2 adsorption-desorption, TEM and EDS, and their catalytic performances in reverse water-gas shift reaction were further investigated. The analyses revealed that MNCAS catalysts displayed the characteristic diffraction peaks of Ni3Mo3N with a good mesoporous structure, in which aggregation caused by Mo2C was effectively improved by the addition of Ni. Moreover, MCAS catalyst exhibited high catalytic activity for the reverse water-gas shift reaction at 300 ℃ with CO selectivity of 93.87%. Meanwhile, MNCAS-8 catalyst [n(AMT):n(HMT) = 1:8, the theoretical and actual loading amount of Mo were 30% and 28.52% respectively, and those of Ni were 5%, and 4.51%, respectively] showed a conversion tendency of CO2 into CH4, the CH4 selectivity reached up to 84.37% at low temperature range, which could be attributed to Ni3Mo3N generated after Ni addition. © 2022, Editorial Office of FINE CHEMICALS. All right reserved.