The highly effective transformation of CO2 into targeted chemicals has attracted significant attention due to greenhouse gas utilization and value-added chemical synthesis functions. Among all of the proposed CO2 transformation pathways, e.g., electrolytic CO2 reduction, photocatalytic CO2 conversion, and thermal-catalytic CO2 utilization, the latter, especially the thermal-catalytic hydrogenation process with renewable energy-driven H2 supply is the most promising strategy owing to its high efficiency, fast reaction rate, controllable product selectivity, and industrial application potential. In recent years, our research group has made great efforts to realize various chemical syntheses from CO2 hydrogenation technology, suchas production of methanol, ethanol, liquid petroleum gas(LPG), alkenes, aromatics (especially para-xylene, PX), etc. We summarize the main achievements of our laboratory in the rational design of novel heterogeneous catalysts and innovative reaction pathways for CO2 hydrogenation, including reaction pathway design for new low-temperature methanol synthesis, catalytic metal-surface interaction tailoring to boost methanol synthesis performance, tandem reaction network fabrication for the synthesis of ethanol, LPG, or aromatics, a capsule catalyst concept for tandem reaction, etc. We want to inspire new ideas and methodologies for the rational design of novel catalysts and reaction pathways for CO2 hydrogenation into value-added chemicals.