The chemical looping methane combustion technology is of great significance to the realization of the sustainable development of energy and environment^{[1, 2]}, and the oxygen carrier design is the core element of this technology^{[3, 4]}. In this work, we performed ab initio DFT+U calculations to elucidate the effect of oxygen vacancies on oxygen migration in the Fe₂O₃ oxygen carrier for the chemical looping process. We explore the effect of oxygen vacancy concentration on oxygen migration and CH₄ dissociation in α-Fe₂O₃(001). DFT calculations show that the increase of oxygen vacancy concentration is beneficial to oxygen migration and CH₄ dissociation in α-Fe₂O₃(001) surface. Then, the oxygen migration rate and CH₄ oxidation rate were compared to explore the rate matching relationship. The fundamental insight into oxygen vacancy effect on CH₄ oxidation with iron oxide oxygen carriers is helpful to design more efficient oxygen carrier catalysts.