Abstract: Chemical conversion of greenhouse gas CO₂ into value-added oxygenates such as ethanol, acetic acid, propanal, propionic acid, butanol, etc. is challenging due to the complexity of C−C coupling and the uncontrollable bonding. In this review, recent research progresses on the synthesis of multi-carbon oxygenates from CO₂ in fixed bed reactor are provided. Firstly, the reaction mechanisms of CO₂ hydrogenation are summarized. Then, the potential catalysts applied in one-step or tandem CO₂ hydrogenation, dry reforming with light hydrocarbons and hydroformylation were introduced over metal carbides, alkali metal modified single or binary metal catalysts such as Cu, Fe, Co, Rh, etc. The reaction mechanism over different catalysts were further elaborated. Finally, the problems and outlook are discussed.