Pure bismuth molybdate (gamma-Bi2MoO6) and multicomponent bismuth molybdate (Co9Fe3Bi1Mo12O51) catalysts were prepared by a co-precipitation method, and were applied to the oxidative dehydrogenation of n-butene to 1,3-butadiene. The Co9Fe3Bi1Mo12O51 catalyst showed a better catalytic performance than the gamma-Bi2MoO6 catalyst in terms of conversion of n-butene and yield for 1,3-butadiene, indicating that the multicomponent bismuth molybdate was more efficient than the pure bismuth molybdate in the oxidative dehydrogenation of n-butene. It was revealed that the crucial factor determining the catalytic performance of Bi-Mo-based catalyst in the oxidative dehydrogenation of n-butene is not the amount of oxygen in the catalyst involved in the reaction (oxygen capacity) but the intrinsic mobility of oxygen in the catalyst involved in the reaction (oxygen mobility). The enhanced catalytic performance of Co9Fe3Bi1Mo12O51 was due to its facile oxygen mobility.