| Summary: | Abstract Alcohols have a wide range of applicability, and their functions vary with the carbon numbers. C6 and C4 alditols are alternative of sweetener, as well as significant pharmaceutical and chemical intermediates, which are mainly obtained through the fermentation of microorganism currently. Similarly, as a bulk chemical, C2 alditol plays a decisive role in chemical synthesis. However, among them, few works have been focused on the chemical production of C4 alditol yet due to its difficult accumulation. In this paper, under a static and semi‐flowing procedure, we have achieved the product control during the conversion of C6 aldose toward C6 alditol, C4 alditol and C2 alditol, respectively. About C4 alditol yield of 20 % and C4 plus C6 alditols yield of 60 % are acquired in the one‐pot conversion via a cascade retro‐aldol condensation and hydrogenation process. Furthermore, in the semi‐flowing condition, the yield of ethylene glycol is up to 73 % thanks to its low instantaneous concentration.
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