Gas-involving cathodic reduction reactions, including hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), and nitrogen reduction reaction (NRR), are key reactions for upgrading abundantly available feedstocks (e.g., H2O, CO2, and N2) into value-added products, and are expected to significantly contribute to sustainable energy conversion and storage technologies. However, the sluggish kinetics of these reactions impede their large-scale applications in real-world scenarios. Perovskite oxides, a promising family of electrocatalysts with great compositional and structural flexibility, have exhibited great potential in these gas-involving reduction reactions with unique catalytic advantages. Thus, current research progress in the application of perovskite oxides as electrocatalysts for these cathodic reactions is comprehensively presented in this review. Initially, a brief discussion on the fundamental characteristics of perovskite oxides and the underlying reaction mechanisms of HER, CO2RR, and NRR are presented. Based on the above foundation, a thorough overview of perovskite oxides adopted for these reactions, with emphasis on the advances in activity, selectivity, stability and modification effects, are then presented. Dedicated subsections explore various performance enhancement strategies with representative examples for each reaction. Finally, concluding remarks summarize the gained insights, current challenges, and propose future directions for designing efficient perovskite oxide electrocatalysts for sustainable energy applications.

https://doi.org/10.1002/aenm.202504986