The development of sustainable chemical processes for the conversion of highly oxygenated biomass feedstocks to chemical products requires efficient and selective processes for partial oxygen removal and refunctionalization. Here we review the development of the deoxydehydration (DODH) reaction, which converts vicinal diols (glycols) to olefins. Uncatalyzed deoxygenative eliminations were first established. The catalyzed DODH reactions have largely employed oxo-rhenium catalysts and a variety of reductants, including PR₃, dihydrogen, sulfite, and alcohols. A variety of glycol and biomass-derived polyol substrates undergo the DODH reaction in moderate to good efficiency, regioselectively, and stereoselectively. Observations regarding selectivity, mechanistic probes, and computational studies support the general operation of a catalytic process involving three basic stages: glycol condensation to an M-glycolate, reduction of the oxo-metal, glycol condensation to produce a metal-glycolate, and alkene extrusion from the reduced metal-glycolate. Recent practical developments include the discovery of non-precious V- and Mo-oxo DODH catalysis.