The syn‐dihydroxylation of olefinic group is one of the most important synthetic transformations which leads to the controlled formation of syn‐diol. Such 1,2‐diol structure is integrated into more complex architectures and substantially participates in the development of biologically active molecules and other fine chemicals. This minireview describes recent evolution of this research field in the past decade, surveying osmium‐free and more eco‐compatible system and in particular the direct oxidation of olefins catalyzed by transition metal complexes.