Alkali-free aluminosilicate glass with SiO₂-Al₂O₃-CaO-ZnO were prepared by high-temperature melting method, and the effects of ZnO/CaO (molar ratio) on the structure, density, elastic modulus and chemical durability of the glass were investigated. The results showed that as ZnO/CaO increased from 0 to 1.07, the density of the glass increased from 2.53 g/cm³ to 2.58 g/cm³. When ZnO/CaO was 0.53, the Vickers hardness of the glass reached the maximum value of 705HV and the coefficient of thermal expansion (CTE) had a minimum value of 3.31×10^-6/℃. When ZnO/CaO was 0, the maximum elastic modulus was 82 GPa and the characteristic point temperature had maximum value: the strain point (T_st) was 778 ℃, the glass transition temperature (T_g) was 792 ℃, and the softening point temperature (T_d) was 855 ℃, respectively. After hydrofluoric acid (HF) or sodium hydroxide (NaOH) corrosion, the weight loss ratio of the glass reached the maximum when ZnO/CaO was 0.53, with the weight loss ratios being 5.05 mg/cm² and 0.9 mg/cm², respectively. All the above property changes exhibited the mixed modifier effect, i.e., due to the difference in radius and field strength magnitude of Zn²⁺ and other ions, ion stacking or site mismatch effects were generated on the glass network structure, resulting in nonlinear changes in glass properties, with positive deviations in density, Vickers hardness, and chemical durability, and negative deviations in modulus of elasticity.