Abundantly available SiO₂ (silica) has great potential as an anode material for lithium-ion batteries because it is inexpensive and flexible. However, silicon oxide-based anode material preparation usually requires many complex steps. In this article, we report a facile method for preparing a SiO₂/C composite derived from coal combustion fly ash as an anode material for Li-ion batteries. SiO₂ was obtained by caustic extraction and HCl precipitation. Then, the SiO₂/C composite was successfully obtained by mechanical milling followed by heat treatment. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). Electrochemical properties were tested using an 18650 cylindrical cell utilizing LiNi_0.8Co_0.15Al_0.05O₂ (NCA) as the counter electrode. Based on the obtained results, the physiochemical characteristics and electrochemical performance, it was determined that SiO₂/C composites were greatly affected by the temperature of heat treatment. The best result was obtained with the SiO₂ content of 10% w/w, heating temperature of 500 °C, initial specific discharge capacity of 586 mAh g⁻¹ at 0.1 C (1 C = 378 mAh g⁻¹), and reversible capacity of 87% after 20 cycles. These results confirmed that the obtained materials had good initial discharge capacity, cyclability, high performance, and exhibited great potential as an anode material for LIBs.