A novel porous silicon composite material (pSi/Ge@Gr/CNTs) was successfully fabricated by utilizing high-energy ball milling and electrostatic assembly techniques. This material starts with a commercial Al₆₀Si₄₀ alloy as the raw material. Through a simple acid etching process, a porous silicon (pSi) matrix was produced. Germanium (Ge) was then introduced into the matrix via ball milling. Finally, with the aid of electrostatic assembly, a dual coating of graphene (Gr) and carbon nanotubes (CNTs) was achieved, endowing the material with a unique structure. The incorporation of Ge introduction effectively augments the conductivity and ion transport characteristics of pSi, substantially bolstering the reversible capacity of the entire electrode. The hybrid encapsulation with Gr and CNTs further fortifies the stability, mechanical robustness, and electrical conductivity of the electrode. When utilized as anodes in LIBs, the pSi/Ge@Gr/CNTs electrode demonstrated outstanding electrochemical performance, achieving a reversible discharge specific capacity exceeding 700 mAh·g^-1 after 100 cycles at a current density of 0.2 A·g^-1, accompanied by a remarkably enhanced rate performance.