Developing eco-friendly approaches to activate C–H bonds in aliphatic alcohols to obtain valuable aliphatic acids remains a challenge. Here, we report an efficient and sustainable method for the selective oxidation of aliphatic alcohols to aliphatic acids via a rationally designed Pt-loaded BiVO4 (BVO) catalyst with enriched surface oxygen vacancies (OVs), achieving 59.2 % of 1-octanol conversion and 80.6 % of 1-octanoic acid selectivity within 6 h in the dark at room temperature. The production rate of 1-octanoic acid under visible light illumination (580.7 µmol/g/h) is 1.85 times higher than that under dark conditions due to the synergistic photo-thermal effect with selectivity as high as 96.2 %. Further investigations indicate that the abundant surface OVs of BVO accelerated the cleavage of HO-H at the defects, facilitating the conversion of aliphatic alcohol at room temperature in the dark. The intrinsic photocatalytic activity of BVO, combined with the synergistic photothermal effect of surface defects and Pt nanoparticles, further promote the conversion of aliphatic alcohols into aliphatic acids, improving conversion and selectivity under visible light illumination. The broad substrate scope highlights the great promise of this approach for aliphatic acid production via photocatalysis under ambient conditions.