<p>The rising demand for energy and environmental concerns necessitate sustainable CO₂ utilization. The electrochemical CO₂ reduction reaction (CO₂RR) has emerged as a promising approach for converting CO₂ into fuels and chemicals. The metal-free carbon materials with nitrogen doping have shown great potential in CO₂RR to produce CO, and pyridinic-N is widely believed to be the responsible active sites. The directed preparation of pyridinic-N dominated carbon and the finely regulation of nitrogen content should be vital for regulating the CO₂RR performance and exploring the catalytic mechanism, which are still challenging. This study developed nitrogen-doped carbon nanotubes (N-CNT) with pyridinic-N domination through pyrolysis of oxidized CNT (OCNT) under ammonia. The nitrogen contents of N-CNT were regulated by adjusting the time for acid-oxidizing treatment, ranging from 5&#xa0;h to 24&#xa0;h. N-CNT with oxidizing time of 24&#xa0;h (N-CNT-24&#xa0;h) demonstrates the highest nitrogen content and the greatest CO₂RR activity among the samples, with a maximum Faradaic efficiency (FE) of 95% for CO production, maintaining FE of 90% over 11&#xa0;h of electrolysis. This research provides insights into selectively introducing Pyridinic-N into CNT and examines the effects of nitrogen doping on catalytic performance, contributing to the design of efficient metal-free carbon-based electrochemical catalysts for CO₂ reduction.</p> Graphical Abstract <p></p>