Catalytic electrodes with the capability to directly convert atmospheric CO 2 into value‐added products are of potential environmental and economic benefit, but entail an effective CO 2 selection strategy to impede the competing O 2 reduction reaction. In this work, we have developed a new generation of hybrid electrodes with improved O 2 tolerance and unprecedented capability of CO 2 conversion to liquid products in the presence of O 2 . We introduce aniline molecules into the pore structure of a polymer of intrinsic microporosity to expand its gas separation functionality beyond pure physical sieving. The chemical interaction between the acidic CO 2 molecule and the basic amino group of aniline renders enhanced CO 2 separation from O 2 . Loaded with a cobalt phthalocyanine‐based cathode catalyst, our hybrid electrode achieves a CO Faradaic efficiency of 71% with 10% O 2 in the CO 2 feed gas. The electrode can still perform CO production at an O 2 /CO 2 ratio as high as 9:1. Switching to a Sn‐based catalyst, we for the first time realize O 2 ‐tolerant CO 2 electroreduction to liquid products, generating formate with nearly 100% selectivity and a current density of 56.7 mA/cm 2 in the presence of 5% O 2 .