It is a potentially desirable process of utilizing CO2 as a feedstock to make valuable chemicals such as methanol. Results from the current study demonstrate Pd modified α-MoC1−x is a high active and selective catalyst for CO2 hydrogenation to methanol. α-MoC1−x is active for both methanol synthesis and RWGS reaction. The addition of 0.1 wt% Pd to α-MoC1−x decreases the CO2 hydrogenation reaction activation energy and increases the CH3OH selectivity due to the H2 spillover effect of Pd. RWGS + CO-hydro pathway as a non-competitive parallel pathway to the dominant formate pathway is verified on Pd/α-MoC1−x/C-N, which increases threefold methanol STY compared with α-MoC1−x/C-N catalyst. This work supplies a feasible strategy for creating a dual active site to enhance the efficiency of methanol synthesis.