AbstractThe reverse water‐gas shift (RWGS) reaction is significant for the resource utilization of CO2. However, this reaction requires high temperatures and metal catalysts are prone to agglomeration, leading to loss of activity. In this work, a Pt catalyst supported on Mo₂N formed via phase transition and metal reverse sintering under a high‐temperature NH₃ atmosphere is developed. This catalyst exhibits excellent RWGS activity, achieving a CO production rate of 294.8 mmolgcat−1 h−1 at 623 K, with CO selectivity maintained at 93%. Moreover, under continuous testing conditions for 100 h, the catalyst's activity shows no significant decline. Notably, further investigation reveals that the surface reaction mechanism at 623 K differs from the previously reported associative mechanism, instead following a redox mechanism in the presence of H₂. This research not only provides a deeper theoretical understanding of the mechanism of CO2 hydrogenation but also offers valuable insights for developing novel and efficient metal catalyst regeneration technologies.