Determining the Si isotopic compositions of samples of the Earth’s surface is crucial to understanding the implications of the biogeochemistry cycling of Si. This study established an alternative method for high-precision Si isotopic measurement in soil samples using gas-source isotope ratio mass spectrometry, which involved the conversion of Si in the samples into SiF4 gas, which was purified cryogenically and collected for isotopic analysis. The proposed method was applied to determine the Si isotopic composition of two reference materials (GBW04421 and GBW04422), and the results were found to be in good agreement with the certified values. Moreover, the proposed method exhibited a long-term measurement precision of 0.05 ‰–0.08 ‰ (2 s) for the δ30Si values. The δ30Si values obtained from ten soil reference materials ranged from −1.84 ‰ to −0.17 ‰, which were within the range of the values reported in the literature (−1.82 ‰ to −0.15 ‰). The sample preparation and analysis method in this study provided an easy and effective approach to determining the Si isotopic composition of solid samples and offers to the promise of being applicable to biogeochemical analyses of the Earth’s surface processes.