The invention provides a gunning material for a carbon-free steel ladle as well as a preparation method and an application of the gunning material. The gunning material is mainly prepared from the following raw materials in parts by weight: 32-35 parts of corundum, 40-45 parts of spinel, 5-12 parts of alpha-Al2O3 fine powder, 8.5-12 parts of a binding agent, 0.09-3 parts of an antiknock agent and 0.01-1 part of a slump retaining agent. The gunning material has the advantages of being good in viscosity, resistant to high-temperature compression and high in fracture resistance and avoiding introduction of carbon impurities. The gunning material for the carbon-free steel ladle can be directly used for performing gunning repair at parts with excessive local melting loss and insufficient residual thickness during cold repair, so that the service life of the carbon-free steel ladle is effectively prolonged, and good molten steel corrosion resistance and erosion resistance are shown in the use process. Refractory consumption of steel per ton can be significantly/remarkably reduced, labor intensity of workers is reduced, economic benefits of enterprises are increased, and the gunning material has great economic significance.