The salient features of bioinert, chemical resistance, and high mechanical strength of synthetic ZrO2 and the bioactivity characteristics of SiO2 has been well-known in biomedical applications. This study has been aimed at the synthesis and quantitative structural analysis of SiO2-stabilized tetragonal ZrO2. The synthesis has been performed through sol–gel technique and the resultant characterization of the powders has been done through X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques. Quantitative analysis on the ZrO2–SiO2 binary oxide systems has been performed by Rietveld Refinement using GSAS-EXPUGI software package. The results from this study have confirmed that SiO2 concentration has played a major role in the stabilization of tetragonal ZrO2. Lower SiO2 concentration has resulted in the formation of mixture of any two different phases comprising of monoclinic ZrO2 (P21/c symmetry) or cubic ZrO2 (Fm-3 m symmetry) or tetragonal ZrO2 (P42/nmc symmetry), whereas higher SiO2 concentration has resulted in the stabilization of single phase tetragonal ZrO2 (P42/nmc symmetry).