Na3VO4 (NVO) nanoparticles were synthesized first by us as a creative anode material for lithium-ion batteries (LIBs). For the purpose of fully demonstrating the potential of NVO for lithium storage, herein, we introduce inexpensive, pollution-free, and scalable biomass carbon to regulate the morphology of NVO, constructing a hybrid of NVO nanoparticles anchored on honeycomb carbon networks (NVO NPs/HCNs). Employed as LIB anodes, NVO NPs/HCNs deliver far superior comprehensive electrochemical properties than those of pure NVO nanoparticles. This is attributed to interconnected carbon networks for improving electrical conductivity and a smaller particle size for reducing the Li+ transfer distance, thus achieving fast reaction kinetics. In addition, the constructed Li-ion full cell with a NVO anode and Li3V2(PO4)3 cathode both using honeycomb carbon networks as the substrate also shows excellent lithium storage properties, opening an avenue to design advanced materials for innovative energy storage technologies.