The invention relates to porous MoO2 photocatalyst microspheres with a hierarchical structure and a preparation method thereof, and belongs to the photocatalyst microspheres and the preparation methodthereof. The porous MoO2 photocatalyst microspheres are composed of a porous outer shell and an inner reticulated porous skeleton. The method comprises the steps: with citric acid as a fuel, ammoniumparamolybdate as a raw material and water as a solvent, carrying out magnetic stirring to form a mixed solution, then, spraying the solution into a tubular furnace with the temperature of 400-500 DEGC by ultrasonic atomization, and obtaining the porous MoO2 photocatalyst microspheres with the hierarchical structure. The preparation system has the advantages of simple operation of technological method, low cost of raw materials, economic feasibility and the like. The catalyst prepared by the method has a special hierarchical structure, and has the hollow and porous morphological characteristics, small particle size, uniform distribution and no agglomeration. The diameter of the microspheres is between 0.5 and 2 [mu]m. The catalyst has good photocatalytic performance and good hydrophilicity, and is beneficial to the application in the fields of photocatalysis, water pollution treatment, lithium ion batteries, supercapacitors, gas sensors and the like.