The invention discloses a composite oxide oxygen carrier and a preparation method and application thereof. The oxygen carrier is a composite metal oxide AxA'l-xBO3 with a perovskite structure, wherein A is rare earth metal lanthanum, A' is transition metallic potassium, B is transition metallic cobalt, and 0.7<x<1. The application of the oxygen carrier in chemical looping combustion technology is that the temperature of combustion in an air reactor is 450-850 DEG C, and the temperature of reduction in a fuel reactor is 450-850 DEG C. The preparation method of the oxygen carrier is that cobalt nitrate, lanthanum nitrate and potassium nitrate are used as a precursor, citric acid or ethylene glycol is used as a complexing agent, a solution is prepared and mixed and stirred evenly, then evaporation of water is conducted, the solution is converted into thick gel from transparent sol, finally drying and baking are conducted, and a sample after baking is the composite metal oxide with the perovskite structure. The oxygen carrier is high in oxygen carrying rate and catalytic activity, strong in carbon deposit resistance and good in stability.