The invention discloses a ceramic cover glaze with luminous effect and a preparation method and application of the ceramic cover glaze. The ceramic cover glaze is prepared from, by weight, 15-40% of transparent frit powder, 15-40% of luminescent powder, 3-5% of Suzhou kaolin, 3-7% of feldspar, 4-8% of glass powder, 3-5% of zirconite powder, 50-70% of stamp-pad ink, 0.1-0.2% of sodium tripolyphosphate, 0.05-0.15% of aluminium-magnesium silicate and 0.2-0.6% of sodium carboxymethylcellulose. The cover glaze is prepared by adjusting the selection of raw material components, optimizing the proportion of the raw material components and using environment-friendly nonradiative materials, the cover glaze is excellent in chemical resistance and has energy-storing and luminous functions, after the cover glaze absorbs light energy, self-Illumination is achieved in the dark, and the decorative art effect of ceramic preparation is enriched in lack of brightness; meanwhile, the glaze surface is fine and smooth and good in texture, it is ensured that the texture of decorative patterns is clear, and the ceramic cover glaze is suitable for design patterns in different styles. The preparation technology is simple, the production efficiency is high, no other devices are added, the firing curve is matched with an existing firing schedule of a furnace, and adjustment is not needed.