AbstractAssembling molecular catalytic centers into crosslinked networks is widely used to fabricate heterogeneous catalysts but they often suffer loss in activity and selectivity accompanied by unclear causes. Here, a strategy for the construction of heterogeneous catalysts to induce activity and selectivity by bottom‐up introduction of segregated electron‐conduction and mass‐transport interfaces into the catalytic materials is reported. The catalytic skeletons are designed to possess different π orderings for electron motion and the open channels are tailored to install finely engineered walls for mass transport, so that origins of activity and selectivity are correlated. The resultant covalent organic framework catalysts with ordered π skeletons and solvophobic pores increase activity by two orders of magnitude, enhance selectivity and energy efficiency by 70‐fold, and broaden the voltage range, to promote CO₂ transformation under ambient conditions. The results open a way to precise interfacial design of actionable heterogeneous catalysts for producing feedstocks from CO₂.