The invention relates to highlight glaze for ancient building porcelain as well as a preparation method and application of the highlight glaze. The highlight glaze for the ancient building porcelain comprises the following components in parts by weight: 20-30 parts of potassium feldspar, 10-15 parts of hollow nanoparticles, 8-10 parts of modified glass beads, 15-20 parts of quartz, 3-6 parts of niobium oxide, 6-8 parts of magnesium oxide, 10-12 parts of a binder, 5-8 parts of barium chromate, 18-20 parts of kaolin and 50-60 parts of water. The preparation method of the highlight glaze for ancient building porcelain comprises the following steps: S1, stirring and mixing potassium feldspar, modified glass beads, quartz, niobium oxide, magnesium oxide, barium chromate, kaolin and water, and performing ball milling to obtain glaze slip; s2, stirring and mixing a binder and the hollow nanoparticles; and S3, uniformly mixing the glaze slip obtained in the step S1 and the mixture obtained in the step S2 to obtain the highlight glaze for the ancient building porcelain. The prepared highlight glaze for ancient building porcelain is smooth in glaze surface, and has excellent glossiness and good mechanical properties.