The invention relates to a CaTiO3/CaO composite material as well as a preparation method and application thereof. The preparation method comprises the following steps: S1, slowly adding a CaCO3 suspension into a TiOSO4 solution which is continuously stirred under a first preset temperature condition, and uniformly stirring to obtain a mixed solution; S2, stirring the mixed solution obtained in thestep S1 under a second preset temperature condition at a constant temperature, dropwise adding a CO (NH2) 2 solution, and adjusting the pH value of the mixed solution to 5-7; and S3, carrying out hydrothermal reaction on the mixed solution obtained in the step S2, and calcining a product of the hydrothermal reaction to obtain the CaTiO3/CaO composite material. According to the method, strong acidand strong alkali are prevented from being used, meanwhile, the cubic CaTiO3 and spherical CaO composite photocatalytic material with uniform particle size distribution is prepared through calcination under the low-temperature condition, and the method has the advantages of energy saving, high production efficiency, environmental friendliness, good product performance and the like.