<p>Carbon dioxide (CO₂) emission significantly impacts global climate change, emerging as a critical developmental issue for humanity. Carbon cycling has been established as an effective strategy to address this challenge. Consequently, the conversion of atmospheric CO₂ into commercially valuable carbon via catalytic reaction pathways presents substantial potential. Rare metals exhibit unique properties, including high-temperature resistance, corrosion resistance, substantial hardness, and commendable electrical and thermal conductivity. Research advancements concerning rare metals have substantiated their potential environmental and economic advantages. Herein, we first summarize the fundamental concepts and applications of electrocatalysis, photocatalysis, photoelectrocatalysis, and photothermal catalysis in CO₂ reduction (CO₂R) reactions (CO₂RRs). The catalysts are classified at the atomic scale, and the influence of catalysts on CO₂RRs at this scale is discussed. Second, we thoroughly examine the relationship between rare metal materials and the selectivity of CO₂R products. Third, we provide a comprehensive overview of the latest advancements in the application of rare metals in CO₂R, as well as the reaction mechanisms of CO₂R catalysts, through the lens of advanced characterization technologies. Finally, we propose potential opportunities and future directions for the development of rare metals in CO₂R.</p> Graphical abstract <p></p>