High-alumina silicate glasses are of interest because of excellent mechanical, optical, and chemical tempering properties, but high melting temperatures can lead to difficulties in removing bubbles and streaks within the glass, which limits the preparation of high-quality glasses. As2O3 is a low-cost and efficient glass clarifier, but As2O3 has been banned due to safety factors. In this paper, sodium calcium glass prepared in a previous study that had solidified 12% (mass fraction) As2O3 was selected as a clarifier, and the effect of the introduction of arsenic-containing soda-lime glass on the network structure of high-alumina silicate glass was analyzed by FTIR spectra and Raman spectra. In addition, the effects of different As2O3 introduction amounts (0% to 0.5%, mass fraction) on the clarification effect of high-alumina silicate glass were investigated by using super depth-of-field microscopy. The results show that the polymerization of the network structure of high-alumina silicate glass decreases with the increase of the addition of arsenic-containing soda-lime glass. In addition, with the increase of As2O3 introduction amount, the bubble defects in high-alumina silicate glass are significantly reduced. When As2O3 introduction amount is 0.5%, the clarification effect is the best, and the bubble fusion ratio is as low as 0.14%.