Conversion of CO2 into chemicals is a promising strategy for CO2 utilization, but its intricate transformation pathways and insufficient product selectivity still pose challenges. Exploiting new catalysts for tuning product selectivity in CO2 hydrogenation is important to improve the viability of this technology, where reverse water-gas shift (RWGS) and methanation as competitive reactions play key roles in controlling product selectivity in CO2 hydrogenation. So far, a series of metal-based catalysts with adjustable strong metal-support interactions, metal surface structure, and local environment of active sites have been developed, significantly tuning the product selectivity in CO2 hydrogenation. Herein, we describe the recent advances in the fundamental understanding of the two reactions in CO2 hydrogenation, in terms of emerging new catalysts which regulate the catalytic structure and switch reaction pathways, where the strong metal-support interactions, metal surface structure, and local environment of the active sites are particularly discussed. They are expected to enable efficient catalyst design for minimizing the deep hydrogenation and controlling the reaction towards the RWGS reaction. Finally, the potential utilization of these strategies for improving the performance of industrial catalysts is examined.