In view of the depletion of fossil fuels, the development and utilization of environment-friendly and sustainable resources widely play an indispensable role in alleviating and resolving problems about resources and environment. Biomass could be utilized as biofuels and renewable platform chemicals. However, biomass-derived molecules are fairly oxygen-rich and hyperfunctionalized. Therefore, new synthetic routes for the regenerative production of chemicals, fuels, and energy from renewable biomass sources are currently investigated especially the transformation high-oxygen-content biomass-derived vicinal diols and poly vicinal alcohols into fuels and value-added chemicals. A range of reductive deoxygenation methods consisting of direct deoxygenation, pyrolysis, hydrogenolysis, decarbonylation, decarboxylation, hydrodeoxygenation, and deoxydehydration (DODH) are under investigation. In this review, we detail the recent-evolutionary and efficient strategies of transition metal-catalyzed DODH of vicinal diols into corresponding alkenes, including rhenium, molybdenum, vanadium, and ruthenium catalysts. Rhenium-catalyzed DODH reactions are very selective and active to provide high yields of olefin products, which keep important functionality in place as well as can be readily functionalized. Recent efforts in rhenium-mediated systems include the development of new rhenium catalysts, the application of cheaper and more available reductants, and growing mechanistic understandings owing to both theoretical and experimental studies. A new emerging trend within DODH is the development of heterogeneous rhenium-based catalysts which demonstrates their ability to rival and in some cases surpass their homogeneous counterparts. Furthermore, catalysts based on the transition metals molybdenum, vanadium and ruthenium show great potential as inexpensive alternatives to rhenium catalysts.