Due to its extremely high theoretical mass specific capacity, silicon is considered to be the most promising anode material for lithium-ion batteries (LIBs). However, serious volume expansion and poor conductivity limit its commercial application. Herein, dealloying treatments of spray dryed Al-Si-Cu-Ni particles are performed to obtain a Cu/Ni co-doped Si-based anode material with a porous nanowire network structure. The porous structure enables the material to adapt to the volume changes in the cycle process. Moreover, the density functional theory (DFT) calculations show that the co-doping of Cu and Ni can improve the capture ability towards Li, which can accelerate the electron migration rate of the material. Based on the above advantages, the as-prepared material presents excellent electrochemical performance, delivering a reversible capacity of 1092.4 mAh g⁻¹ after 100 cycles at 100 mA g⁻¹. Even after 500 cycles, it still retains 818.7 mAh g⁻¹ at 500 mA g⁻¹. This study is expected to provide ideas for the preparation and optimization of Si-based anodes with good electrochemical performance.