The development of lithium-ion batteries (LIBs) is still facing challenges due to the design and optimization of anode materials and their Li-ion storage mechanisms. In this study, we aimed to address this issue by constructing three-dimensional hierarchical heterojunction structures using a double needle electrospinning strategy. The heterostructure was composed of insertion-type Li3VO4 and conversion/alloying-type Ga2O3 embedded porous carbon nanofibers (Li3VO4-Ga2O3@PCNF). The designed heterostructured Ga2O3 and Li3VO4 materials were found to effectively enhance charge transfer dynamics, thereby improving capacity and rate capability. Additionally, the facilitated efficient contact between the electrode and electrolyte, enabling the diffusion of ions and electrons. When applied as an anode material in LIBs, the Li3VO4-Ga2O3@PCNF composite achieved a high capacity of 630.0 mA h g-1 at 0.5 A g-1, and full capacity recovery after 6 periods of rate testing over 480 cycles. When simulating the practical application under a high discharge current of 6.0 A g-1, the Li3VO4-Ga2O3@PCNF could still deliver a high discharge capacity of 322.0 mA h g-1 after 2000 cycles. Furthermore, the composite exhibited a remarkable capacity retention of 77.2% after 2000 cycles at 6.0 A g-1. This research provides valuable guidance for the design of high-performance Li3VO4-based anodes, particularly in addressing the issue of inferior electronic conductivity.