Solar‐driven reduction of CO2, which converts inexhaustible solar energy into value‐added fuels, has been recognized as a promising sustainable energy conversion technology. However, the overall conversion efficiency is significantly limited by the inefficient charge separation and sluggish interfacial reaction dynamics, which resulted from a lack of sufficient active sites. Herein, Bi12O17Cl2 superfine nanotubes with a bilayer thickness of the tube wall are designed to achieve structural distortion for the creation of surface oxygen defects, thus accelerating the carrier migration and facilitating CO2 activation. Without cocatalyst and sacrificing reagent, Bi12O17Cl2 nanotubes deliver high selectivity CO evolution rate of 48.6 μmol g−1 h−1 in water (16.8 times than of bulk Bi12O17Cl2), while maintaining stability even after 12 h of testing. This paves the way to design efficient photocatalysts with collaborative optimizing charge separation and CO2 activation towards CO2 photoreduction. Defect‐rich Bi12O17Cl2 superfine nanotubes were prepared for the photocatalytic reduction of CO2. Benefiting from the superfine nanotube structure to accelerate charge separation and oxygen defects to facilitate CO2 activation, the Bi12O17Cl2 nanotubes displayed a CO formation rate of 48.6 μmol g−1 h−1 in water without cocatalyst and sacrificial reagent, which is roughly 16.8 times that of bulk Bi12O17Cl2.