In this study, amorphous SiO2 is used to coat GaIn nanodroplets (GaIn NDs) to construct the core-shell structure of GaIn@SiO2 nanodroplets (GaIn@SiO2 NDs). We found that the amorphous SiO2 shell (~12 nm) formed a stable solid electrolyte interface (SEI) film, alleviated the volume expansion, and provided electron/ion transport channels to achieve excellent cycling performance and high specific capacity. The resulting GaIn@SiO2 NDs exhibited high capacities of 562, 541, 523, 502, 494, and 456 mAh g−1 at 0.1, 0.2, 0.5, 1, 2, and 5 C, respectively. The capacity of 330 mAh g−1 at 1 C was observed after more than 500 cycles. In situ X-ray diffraction (in situ XRD) was used to explore the lithiation mechanism of the GaIn anode during discharge. This study elucidates the design of advanced liquid alloy-based anode materials for high-performance lithium batteries.