To address the limitations of the current anodes of Li+-ion batteries (LIBs), a Ge/GeO2/Carbon (Ge@GeO2-C) composite was designed by introducing a high-energy ball-milling process for advanced LIBs. Ge@GeO2-C is prepared and characterized by XPS, XRD, SEM, and TEM, which facilitate synthesis and provide controllability with respect to milling time. Interestingly, as the ball-milling time increased, the proportion of metallic Ge increased during the carbon thermal reduction reaction. The electrochemical characteristics of Ge@GeO2-C are assessed using differential capacity analysis (dQ/dV) and galvanostatic charge-discharge techniques to confirm its viability as an anode material in LIBs. The results demonstrated decent initial and secondary capacities of approximately 1800 mAh g-1 (for the first cycle) and 838 mAh g-1 (for the second cycle) at a rate of C/60 by the reaction between Ge and the Li-Ge complex. Furthermore, postmortem characterization was performed to gain an understanding of the material, suggesting future prospects for advanced LIBs.