Porous Polyimides (pPIs) represent a fascinating class of porous organic polymers (POPs). Not only do they exhibit high thermal and chemical stabilities, high surface areas, and energy storage capabilities, but...

A series of porous polyimides (pPIs) are synthesized, and their surface areas and pore sizes are optimized by the previously reported Bristol–X'an‐Jiatong (BXJ) approach. How this approach can be used to tune and optimize the porous network properties to target and tune their ability to capture CO2 is demonstrated. Once optimized, these porous organic frameworks are utilized, for the first time, as electrocatalysts for the conversion of CO2. The excellent Faradaic efficiencies (FEs) for the conversion of CO2 to formate (91%) and methanol (85%) present exciting opportunities for the metal‐free generation of useful fuels and feedstocks from CO2. In addition, the ability to directly address and select the conversion products through tuning of the porous materials’ properties highlights the potential of this approach, and more generally for a wide range of organic frameworks as future metal‐free CO2 reduction catalysts.