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Solid oxide fuel cell (SOFC) possesses outstanding advantages of broad fuel sources and high energy conversion efficiency. It is considered one of the most promising clean energy technologies in the future. At present, the hot spot of SOFC research is to reduce the working temperature to 500 ~ 800℃ low temperature zone. This can reduce the operating cost, increase the reliability and accelerate the commercialization process of SOFC. The cathode is an important component of SOFC. It is very important to design and optimize cathode materials with high activity for oxygen reduction reaction. The electron-ion mixed conductive (MIECs) oxide with perovskite structure or layered structure derived from perovskite structure are the most studied SOFC cathode materials. First principles can compensate for the lack of experimental information. It has proved to be a powerful tool to elucidate reaction mechanism as the technique can provide electronic structure, geometrical parameters, adsorption energy and transition state information. It can provide scientific basis and theoretical guidance for rational design and development of high performance new SOFC cathode materials. This article reviewed the formation and migration of oxygen vacancies in perovskite cathode and the adsorption, the dissociation, the transmission process of oxygen on the cathode surface (including the introduction of precious metals) and summarized our previous research results. Finally, the problems of current research and the future research direction of perovskite cathode simulation are summarized and prospected.