Hydrogenation of CO₂ to methanol utilizing the hydrogen from renewable energy sources offers a promising way to reduce CO₂ emissions through the CO₂ utilization as a carbon source. However, it is a challenge to convert CO₂ to methanol with high activity and high methanol selectivity. Herein, we report a class of metal-oxide solid-solution catalysts: M_aZrO_x (M_a = Cd, Ga), which show a methanol selectivity up to 80% with the CO₂ single pass conversion reaching 4.3%-12.4% under the reaction conditions of H₂/CO₂ = 3/1, 24※000 h^-1, 5 MPa. Structural and electronic characterizations combined with denisty functional theory calculations suggest that the M_a and Zr components in M_aZrO_x (M_a = Cd, Ga) solid-solution catalysts show a strong synergetic effect, which enhances the H₂ heterolytic dissociation and results in high activity and high methanol selectivity. The solid-solution catalyst with dual metal oxide components offers an approach for the selective hydrogenation of CO₂ to chemicals.