The electrochemical C-N coupling of CO2 and nitrogenous species provides a promising approach for synthesizing valuable chemicals such as urea, amides, and other C-N compounds. However, the unbalanced formation of C- and N-intermediates results in slow C-N coupling kinetics. Herein, we report an atomically Pd-bridged Cu/Cu2O (Pd1-Cu/Cu2O) catalyst, synthesized through the in situ electrochemical reconstruction of Pd1-Cu2Te nanosheets. This catalyst features Pd-Cu dual sites that significantly enhance C-N coupling both thermodynamically and kinetically. The reconstructed Pd1-Cu/Cu2O achieves a urea yield rate of 31.8 mmol h-1 gcat.-1 and a Faradaic efficiency (FE) of 42.2%, along with excellent stability over 100 h. In situ spectroscopic examinations and theoretical calculations disclose that the Pd-Cu dual sites on Pd1-Cu/Cu2O modulate the reduction kinetics of CO2 and NO3-, balance the formation of crucial *CO and *NH2 intermediates, and lower the energy barrier for C-N coupling, thereby facilitating urea synthesis. Furthermore, the Pd1-Cu/Cu2O enables the unprecedented C-N coupling of aniline with CO, resulting in a remarkable acetanilide yield rate of 1021.2 mmol h-1 gcat.-1 with an FE of 23.7%. This heteroatom bridging strategy offers a new pathway for designing efficient electrocatalyst for the synthesis of C-N coupled compounds.