Due to the easy accessibility, chemical stability, and structural tunability of the macrocyclic skeleton, cobalt phthalocyanines immobilized on carbon supports offer an ideal research model for advanced electrochemical carbon dioxide reduction reaction (eCO2RR). In this work, an amphiphilic cobalt phthalocyanine (TC‐CoPc) is loaded on multiwalled carbon nanotubes to reveal the roles of hydrophilic/hydrophobic properties on catalytic efficiency. Surprisingly, the resultant electrode exhibits a CO Faradaic efficiency (FECO) of 95% for CO2RR with turnover frequency (TOF) of 29.4 s−1 at an overpotential of 0.585 V over long‐term electrolysis in a H‐type cell. In the membrane electrode assembly (MEA) device, the boosted transport of water vapor to the catalyst layer slows down carbonate crystallization and enhances the stability of the electrode, with FECO value of >99% over 27 h at −0.25 A, representing the best selectivity and stability among reported molecular catalysts in MEA devices. The amphiphilic cobalt phthalocyanine, which decreases interfacial charge and mass transfer resistance and maintains effective contact between active sites and the electrolyte, highlights the exceptional CO2 conversion from a molecular perspective.