Abstract The renewability of glycerol has made it an appealing medium for the processing of various compounds. Selective dehydration of glycerol to acetol is one of the promising glycerol valorizations. The performance and recent progress of those typical and most frequently mentioned catalysts for the synthesis of acetol from glycerol, including noble metals and transition‐based metals, are summarized in detail. A Cu‐based catalyst is identified as an appropriate catalyst for the synthesis of the glycerol dehydration route. In addition, advances in process development of several solid supports, the effects of catalyst preparation methods of suitable supports on catalytic activity, and the performance of catalysts' considering the catalytic conversion of glycerol to acetol are reviewed.