 This study introduces a new method of modifying metalloporphan metal organic frameworks, MOFs, by adding hexamethylene tetramine, HMTA, to create site-specific functionalized electrocatalysts. These modified electrocatalysts were then used in light-assisted CO2 electroreduction. The results showed that the modified electrocatalysts had significantly increased CO2 adsorption enthalpies and electrochemical active surface areas compared to their unmodified counterparts. Additionally, the modified electrocatalysts displayed improved CO2 electroreduction performance when illuminated with light. The theoretical calculations confirmed that the oriented coordination of HMTA increased the charge density of the active sites, which resulted in a doubling of the CO2 adsorption energy and a reduction of the energy barrier for the reaction, leading to improved CO2 electroreduction performance. This article was authored by Jifeng XIN, Shwedong, Yerong Wang, and others. We are article.tv. Links in the description below.