Methods for producing butadiene by the oxidative dehydrogenation of butene are provided. Methods for producing butadiene from a feed stream including oxygen and butene in a molar ratio of oxygen to butene (O2/C4H8) from about 0.9 to about 1.5 can include introducing the feed stream to a catalyst in the presence of steam. The molar ratio of steam to butene (H2O/C4H8) can be from about 10 to about 20. Methods can further include reacting the butene to generate a product stream therefrom comprising butadiene and water. Methods can further include separating water from the product stream to generate a butadiene stream including greater than about 85 wt-% butadiene.