The catalytic conversion of waste CO2 into valuable fuels and chemicals is a promising avenue for environmental protection and economic growth. A research team from the University of Science and Technology of China, part of the Chinese Academy of Sciences, led by Prof. Jiang Hailong and Prof. Jiao Long, has made significant progress in this area by developing an innovative approach to enhance electrochemical CO2 reduction. Through the use of catalytically active Co(salen) units and pyridyl-substituted alkyl carboxylic acids co-grafted onto metal-organic framework nanosheets, the team achieved precise control over the microenvironment around catalytic sites at an atomic scale. This novel strategy led to the stabilization of *COOH intermediate, overcoming a key energy barrier and significantly improving the efficiency of CO2 reduction. The optimized catalyst, Co&p-PyC3/MOFNs, demonstrated exceptional catalytic activity and selectivity in converting CO2, outperforming other catalysts. The researchers also observed the in situ reduction of pyridine to PyrH• during the reaction, which played a crucial role in enhancing performance. By creating a triad intermediate involving *COOH, trifluoroethanol, and PyrH• through hydrogen-bonding interactions, the team successfully minimized the reaction energy barrier, providing insights into the microenvironment's role in catalysis optimization. This study underscores the importance of microenvironment modulation for advancing catalytic processes and offers a significant contribution to the field of CO2 conversion.