The bulk oxygen transfer and surface reaction as important parts of the chemical looping-related process are crucial for the rational design of new redox catalysts. This paper describes an experimental study on the effect of bulk oxygen transfer and surface reaction in Ce1–xxO2 supported VOx redox catalysts for the chemical looping oxidative propane dehydrogenation reaction. It was found that the introduction of Zr dictates the reaction performance of the redox catalyst by modulating the bulk oxygen transfer and surface reaction. The kinetic study reveals that the instantaneous reduction rate of the redox catalysts is determined by the H-abstraction step in the surface reaction. The introduction of Zr can reduce the activation energy of the H-abstraction step, which leads to the enhancement of the instantaneous reduction rate. Meanwhile, the oxygen supply capacity of the cerium oxide is increased by Zr, allowing the surface reaction to proceed over longer durations. Furthermore, the reaction model derived from the kinetics study is validated using a number of (quasi) in situ techniques. This study provides fundamental insights into the role of bulk oxygen transfer and surface reaction in chemical looping or related process.