A new catalyst of Cd/TiO2, enabling 81% methanol selectivity at 15.8% CO2 conversion with the CH4 selectivity below 0.7% was discovered. The combination of experimental and computational studies show that the unique electronic properties of Cd cluster supported on TiO2 are responsible for the high selectivity for CO2 hydrogenation to methanol via a HCOO* pathway realized at the interface catalytic sites.