Structural reconstruction is commonly observed during electrocatalytic CO₂ reduction (CO₂RR) process. However, the proper modulation of interface and defect sites remains challenging with the mechanism understanding to realize the favorable electrocatalysis. Herein, the atomic bridging of bismuth with indium atoms is elaborately designed for improving electrocatalysis of CO₂RR via electrochemical reduction and in situ anchoring strategy. As revealed by in situ structure analysis and theoretical studies, the ensemble sites supported on carbon matrix enable the charge density gradient to significantly promote the adsorption of *OCHO intermediate by the regulation of σ bonding and π* back-donation. Consequently, such unique electrocatalyst achieves the high formate faradaic efficiency of 95.1% over the entire potential range tested and the long-lived stability for 9 d. With coupling of CO₂RR, the solar-driven full cell demonstrates the spontaneous production of formate and 2,5-furandicarboxylic acid via the efficient oxidation of 5-hydroxymethylfurfural with an outstanding yield of 88.2%, highlighting the impressive solar-to-fuel conversion selectivity. Monitoring and understanding the intrinsic active sites of biatomic bridge are crucial to elucidate the synergic electrocatalysis for rationally designing high-performance electrocatalysts.

_{在电催化 CO 2}还原 (CO ₂ RR) 过程中通常会观察到结构重建。然而，界面和缺陷位点的适当调制仍然具有挑战性，需要了解机制才能实现有利的电催化。在此，精心设计了铋与铟原子的原子桥接，以通过电化学还原和原位锚定策略改进 CO ₂ RR的电催化。据现场透露结构分析和理论研究表明，碳基质上支持的集合位点使电荷密度梯度能够通过调节 σ 键合和 π* 回馈显着促进 *OCHO 中间体的吸附。因此，这种独特的电催化剂在整个测试电位范围内实现了 95.1% 的高甲酸法拉第效率和 9 天的长寿命稳定性。_{与CO 2}偶联RR，太阳能驱动的全电池展示了通过 5-羟甲基糠醛的有效氧化自发产生甲酸盐和 2,5-呋喃二甲酸，产率为 88.2%，突出了令人印象深刻的太阳能到燃料的转化选择性。监测和了解双原子桥的固有活性位点对于阐明协同电催化以合理设计高性能电催化剂至关重要。