AbstractEfficient and selective CO₂ electroreduction into chemical fuels promises to alleviate environmental pollution and energy crisis, but it relies on catalysts with controllable product selectivity and reaction path. Here, by means of first-principles calculations, we identify six ferroelectric catalysts comprising transition-metal atoms anchored on In₂Se₃ monolayer, whose catalytic performance can be controlled by ferroelectric switching based on adjusted d-band center and occupation of supported metal atoms. The polarization dependent activation allows effective control of the limiting potential of CO₂ reduction on TM@In₂Se₃ (TM = Ni, Pd, Rh, Nb, and Re) as well as the reaction paths and final products on Nb@In₂Se₃ and Re@In₂Se₃. Interestingly, the ferroelectric switching can even reactivate the stuck catalytic CO₂ reduction on Zr@In₂Se₃. The fairly low limiting potential and the unique ferroelectric controllable CO₂ catalytic performance on atomically dispersed transition-metals on In₂Se₃ clearly distinguish them from traditional single atom catalysts, and open an avenue toward improving catalytic activity and selectivity for efficient and controllable electrochemical CO₂ reduction reaction.