In this paper, raw glazes from the SiO2–Al2O3–CaO–MgO–K2O–Na2O system were examined. Zirconium oxide, in five different amounts – 1.5, 3, 6, 12 and 24 wt%, was added to the chosen system and heat treated at 1230 °C, where they were kept for an hour. The addition of zirconium oxide, especially in greater amounts, caused the crystalline phase of zirconium silicate and intact ZrO2 grains to appear. The amounts of these crystalline phases indicate that zirconium cations are present in the amorphous phase. Analysis of structural measurements showed that zirconium ions (Zr4+) have a depolymerizing effect on the glassy matrix of the glazes; however, it does not change subnets of an aluminum-silicon subnetwork. This is a new perspective on the matter, because it confirms that the addition of zirconium oxide causes those ions to be present not only in crystalline phases, but also some Zr4+ cations are located in the aluminosilicate subnetwork (Si–O–Si(Al)), in interstitial spaces, and it interacts only with silicon-oxygen bonds. Measurements of the color in the CIE L*a*b* system of the obtained glazes confirmed that the addition of zirconium oxide results in glaze with significantly higher whiteness (L* parameter increases) and a more monochromatic color (a* and b* parameters tend toward zero). The results of the surface smoothness were also presented, which clearly confirm that the higher content of zirconium crystalline phases results in obtaining a surface with higher roughness.