The study of the chemical composition of historical glasses is widely used in archaeometry. The results of such analyses provide information on the probable date, place, and technological features of their production. Over time, a weathered layer may form on the surface of the glass, which differs in composition from the original one. To determine the initial composition using conventional methods (for example, X-ray fluorescence spectroscopy), the weathered layer should be removed. For historical objects, such manipulation is unacceptable and should be minimized. One of the methods for analyzing the chemical composition with minimal damage to a sample is laser-induced breakdown spectroscopy. The aim of this work was to develop a LIBS method, which makes it possible to perform a quantitative analysis of lead silicate glasses, including glasses containing a weathered layer. Reference glasses with a variable content of potassium, silicon, and lead oxides were synthesized, and based on the LIBS spectra, a calibration dependence was obtained that made it possible to measure the concentration of lead and potassium oxides in glasses within 70–85 and 5–20 wt%, respectively. The method was applied to analyze the composition of the glaze on a historic glazed tile from the burial church in the Euphrosinian monastery in Polotsk (the second half of the 12th century AD). The crater formed with the laser beam on the glazed surface was about 200 microns. Such damage is negligible compared to the total surface area of the tile (~10 cm²). The thickness of the weathered glaze layer was 70 microns, which was determined using variation in lead oxide content.