ABSTRACT Rechargeable Li‐CO 2 batteries (LCBs) hold great promise for dual‐function CO 2 utilization and energy storage, yet their practical application is hindered by the sluggish kinetics of the conventional Li 2 CO 3 pathway, resulting in low discharge voltages (below 2.0 V) and large overpotentials (over 1.0 V). Herein, we propose a strategy of CO 2 reduction pathway engineering via alloy‐support interaction to unlock high‐performance LCBs. We designed a Ru 2 Cu 4 /NC 1000 catalyst, where sp