Glass structure tailoring of alkali silicate glasses by addition of ZrO2 and Er2O3 is found to enhance the chemical durability of glasses. ZrO2 (x ranged between 5 mol% to 15 mol%) and Er2O3 (y ranged between 0.5 mol% to 1.5 mol%) were used to replace SiO2 and Na2O, respectively, in the glasses with the nominal composition of 10Li2O-(15-y)Na2O-10CaO-(65-x)SiO2-xZrO2-y Er2O3. The samples were prepared by conventional melt quenching technique. The structures of produced glasses were examined by X-ray absorption spectroscopy (XAS) and Raman spectroscopy. XAS spectra demonstrated that the oxidation numbers of Zr and Er ions were +4 and +3, respectively. The chemical environment around both cations was six-fold coordination. In addition, Raman spectra demonstrated that the Zr4+ ions formed the Q4(Zr) structure, which caused the reduction of non-bridging oxygen. In case of the Er3+ ions, the formation of the Si-O-Er bonds was explained from the Raman study. The chemical durability of glass was determined from Na+ ions leaching values. In pH 7 solution, the leached Na+ ions reduced from 25.67% to 21.43% and from 22.50% to 20.49% as a function of concentration of ZrO2 (x = 5 mol% to 15 mol%) and Er2O3 (y = 0.5 mol% to 1.5 mol%), respectively. As the results, the chemical durability of the ZrO2-containing and Er2O3-containing glasses were significantly improved due to charge compensated mechanism and enhancing network rigidity by increasing cation field strength. Moreover, the micro-hardness (580 HV to 837 HV) and density (2.54 g⸳cm-3 to 2.82 g⸳cm-3) also displayed an increased tendency with larger concentration of ZrO2 and Er2O3.