Addressing the volume expansion when silicon and metal oxides alone are used as anode materials for lithium-ion batteries. This study used a simple self-assembly method and electrostatic spinning technique to prepare silicon@copper oxide@carbon nanofibres (CNFs) anodes with dual modification. The high rigidity of metal oxide CuO and the excellent cycling stability of CNFs effectively reduce the buildup of silicon particles, alleviate the volume expansion effect, and improve the electrical conductivity, which leads to better cycling stability and larger specific capacity of lithium-ion batteries. An excellent reversible specific capacity of 748.5 mAh g-1 was observed after 800 cycles at a high current density of 1Ag-1. In addition, the surface of Si@CuO@CNFs electrodes remains smooth and undamaged after 800 cycles, and the increase in cross-sectional thickness is about 68%, which is significantly smaller than the 300% increase in cross-sectional thickness of pure Si anode and effectively improves the specific capacity of Li-ion batteries. This research optimizes the design of silicon-based anode materials with simple and mature process technology, which makes an indispensable contribution to developing high-efficiency, long-life, and environmentally friendly lithium-ion batteries. The easy availability and non-polluting nature of the materials used also effectively reduce the reliance on rare or expensive elements, minimize the production process's environmental impact, and vigorously promote the global energy transition and low-carbon green development strategy.