Hydrogenation of CO2 into valuable chemicals is in great demand but still challengeable. Here we report the selective hydrogenation of CO2 into ethanol over non‐noble cobalt catalysts (CoAlOx), presenting a significant advancement for the conversion of CO2 into ethanol as a major product. By adjusting the Co‐CoOx composition of the catalysts under different pre‐reduction temperatures, the efficiency of CO2 hydrogenation to ethanol was well optimized over the catalyst reduced at 600 °C, giving ethanol selectivity of 92.1% at 140 °C with the ethanol time yield at 0.444 mmol g‐1 h‐1. Operando FT‐IR spectroscopy reveals that the high selectivity of ethanol over the CoAlOx catalyst is ascribed to the formation of acetate from formate with the insertion of *CHx, the key intermediate to produce ethanol from CO2 hydrogenation. The full paywalled article is available on the Angewandte Chemie website at https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201800729