The invention relates to a water-soluble non-combustible ceramic anti-radiation coating and a preparation method thereof. The coating comprises an active material, an inorganic filler, a shrinkage reducing agent, a thickening agent, a flame retardant, a silicate binder, a reflection reinforcing agent and an aid in a mass ratio of (2-2.8):(0.5-1):0.40:(0.01-0.04):(0.4-0.8):2.13:(0.067-0.2):0.3. The coating is formed by fully mixing the components uniformly and can be used for painting or spraying, and a layer of modified fluoro-silicone emulsion is painted on the surface of the coating after the coating is surface-dried. The coating can be used as an exterior wall coating (base coat), and also can be used as a protective coating for the surfaces of an exterior wall thermal insulation plate, mortar, a sintered brick and a building enclosure structure; and the water-soluble ceramic coating has the characteristics of high durability, light weight, high strength, high efficiency, flame retardance, fire resistance, controllable quality, water resistance, alkali resistance, freezing and thawing resistance, cracking resistance, falling resistance and the like.