Although the silicon oxide (SiO₂) as an anode material shows potential and promise for lithium-ion batteries (LIBs), owing to its high capacity, low cost, abundance, and safety, severe capacity decay and sluggish charge transfer during the discharge–charge process has caused a serious challenge for available applications. Herein, a novel 3D porous silicon oxide@Pourous Carbon@Tin (SiO₂@Pc@Sn) composite anode material was firstly designed and synthesized by freeze-drying and thermal-melting self-assembly, in which SiO₂ microparticles were encapsulated in the porous carbon as well as Sn nanoballs being uniformly dispersed in the SiO₂@Pc-like sesame seeds, effectively constructing a robust and conductive 3D porous Jujube cake-like architecture that is beneficial for fast ion transfer and high structural stability. Such a SiO₂@Pc@Sn micro-nano hierarchical structure as a LIBs anode exhibits a large reversible specific capacity ~520 mAh·g⁻¹, initial coulombic efficiency (ICE) ~52%, outstanding rate capability, and excellent cycling stability over 100 cycles. Furthermore, the phase evolution and underlying electrochemical mechanism during the charge–discharge process were further uncovered by cyclic voltammetry (CV) investigation.