Selective oxidation of alcohols plays a significant role in chemical synthesis and industrial production. Compared with aromatic alcohols, which are readily transformed into aldehydes, selective oxidation of aliphatic alcohols is more challenging due to its poor activity and low selectivity. Here, we report unprecedentedly selective oxidation of a number of aliphatic alcohols over bismuth oxyhalide photocatalysts, investigating the optical and electrochemical properties of bismuth oxyhalide and demonstrating the oxidation performance of three main aliphatic alcohols to the corresponding aldehydes. BiOCl showed excellent catalytic performance, with over 90% conversion and nearly 100% selectivity at room temperature using molecular oxygen. Meanwhile, proposed photocatalytic oxidation mechanism presented that molecular oxygen is not only activated to generate superoxide radicals, but also interact with substrate and catalysts. This work provides a new approach for selective oxidation of aliphatic alcohols and triggers more enthusiasm in contributing to the selective oxidation of aliphatic alcohols.