The Li3V2(PO4)3/phosphorus-doped carbon (LVP/P-C) nanocomposites with multilevel structures (such as spheroidal, foam, prism and flower-like structures) are synthesized via one-pot in-situ synthesis using hybrid vanadium metal-organic frameworks (V-MOFs) as precursor. The structure and morphology of the LVP/P-C nanocomposites were characterized by scanning electron microscopy, transmission electron microscopy, Raman, X-ray diffraction and element mapping. The results show that the multilevel structures are generated from the assemblies of the hybrid surfactant templates in the glass fiber drawing wastewater (GFDW) and the hybrid V-MOFs. The structure of LVP/P-C nanocomposite is controlled by V-MOFs. The nanocomposites exhibit a long service life, a discharge capacity of 65 mA h g−1 at 10 C with 90% capacity retention after 1100 cycles. The high cycling stability is attributed to the multilevel structures, which is ideal for making rechargeable lithium ion batteries. More importantly, our results have demonstrated that GFDW can be transformed into treasure of multilevel structure nanocomposites for cheap Li ion batteries.