The oxidative dehydrogenation of n-butane was investigated over a highly selective (Ni, Fe, Co)-Bi-O/y-Al2O3 catalyst with kinetic studies. The transient response method with (O)(2) concentration was also utilized to study the oxygen species responsible for dehydrogenation and cracking pathways. Power law models were utilized for the reactions. The activation energies were obtained in the order 34.4 < 68.8 < 88.5 kJ/mol, and pre-exponential factors of 0.857, 1.930, and 0.198 mol/g(cat). min for the first-step dehydrogenation, second-step dehydrogenation, and cracking, respectively, were obtained. The quantitative fixation reveals that the butadiene selectivity mainly reflects the pre-exponential factor as the concentration/accessibility of the active sites.