The invention provides a preparation method of a copper oxide surface composite Mn oxidation layer material. The preparation method comprises the following steps: in water, an alcohol, or a water-alcohol mixed solution, redox displacement is performed between a soluble Mn source compound containing a +7-valent oxidation-state Mn element (Mn(VII)), such as KMnO4, and the surface of a Cu2O matrix, so that a novel method for compositing a Mn oxidation layer (poly-valent Mn oxides coexist and are marked as MnOx) on the Cu2O surface can be obtained; and heat treatment is performed, so that a CuO surface composite MnOx material can be further obtained. The preparation method has the characteristics that MnOx can be highly dispersedly, uniformly and closely composited on the Cu2O or CuO material surface as the molecular-scale thin layer; the structure and the performance of the copper oxide surface composite Mn oxidation layer material is mainly determined by the chemical mole ratio of the Mn element and Cu2O, and the series control of a sample is easy to achieve; the ratio range involved in the preparation method is 0.02-1.0; the Cu-Mn composite structure or interface interaction research and application fields are concerned; and the preparation method can provide a reference for the development of a high-temperature material.