The invention discloses luminescent glaze for enamel painted porcelain and a preparation method and application thereof. The luminescent glaze for enamel painted porcelain comprises basic glaze for the enamel painted porcelain and a protective-glaze luminescent material, wherein the protective-glaze luminescent material is prepared by firstly mixing and then repeatedly braking the flux for the protective-glaze luminescent material and a luminescent material, and the flux for the protective-glaze luminescent material comprises the following components in percentage by weight: 42-48 percent of SiO2, 3-7 percent of SrO, 15-21 percent of B2O3, 0.2-1.2 percent of Al2O3, 3-7 percent of Li2O, 2-7 percent of Na2O, 1-3 percent of K2O, 0.6-3.8 percent of metal fluoride, 2-3.5 percent of P2O5, 0-0.5 percent of Ta2O3, 0-1 percent of Nb2O5, 0-0.5 percent of ZrO2, 0-3 percent of CeO2, 0-0.5 percent of La2O3, 0-2 percent of Y2O3, 5-10 percent of ZnO, and 0-5 percent of MgO. According to the luminescent glaze for the enamel painted porcelain provided by the invention, the thermal stability and luminescence properties of the luminescent material can be guaranteed so as to improve the luminance and luminous time of the prepared painted porcelain after irradiation, while the various characteristics of the traditional enamel painted porcelain can be maintained.