AbstractA CO2 hydrogenation reactor based on protonic ceramic electrolysis cells (PCECs) is one of the most promising options for the efficient and clean conversion of CO2. However, insufficient performance and durability have hindered the practical application of such CO2 hydrogenation reactors. Here, fabricates a large‐area (≈10 cm2) tubular air electrode supported PCEC (AES‐PCEC) and develop a fuel electrode regeneration strategy for efficient and durable CO2 hydrogenation. The AES‐PCEC demonstrates a CO yield of 2.88 mL min−1 at 650 °C while maintaining excellent durability for over 1100 h. The high stability of the AES‐PCEC can be attributed to the robust and thin fuel electrode structure as well as the water‐mediated carbon removal regeneration mechanism. Density functional theory calculations have confirmed the regeneration mechanism facilitated by the excellent water hydration and dissociation capability of the BaCe0.4Zr0.4Y0.1Yb0.1O3‐σ. This work offers a feasible strategy to design high‐performance and durable PCEC‐based CO2 hydrogenation reactors.