One aspect of the invention relates to a dehydrogenation catalyst composite containing alumina, chromium oxide, lithium oxide, and sodium oxide. The invention also relates to methods of making the dehydrogenation catalyst composite. Another aspect of the invention relates to method of dehydrogenating a dehydrogenatable hydrocarbon involving contacting the dehydrogenatable hydrocarbon with a dehydrogenation catalyst composite containing alumina, chromium oxide, lithium oxide, and sodium oxide to provide a dehydrogenated hydrocarbon, such as an olefin.