Electrode materials can display superior electrochemical performances and behavior via the nanoscale design. Here, the low-temperature synthesis of nano-glass ceramics (NGCs) is based on inheriting the network structure of yeast polyphosphate metabolism. The NGCs-3 sample synthesized with a molar ratio of Fe/V = 7:6 is composed of nano-domains of semiconducting oxide glass (Li2O-Na2O-Fe2O3-V2O5-P2O5, LNFVP), nanocrystalline particles (Li9Fe3P8O29, Li0.6V1.67O3.67 and VOPO4), and nanopores connected by interfaces. We have clarified the mixing ion transport mechanism and the electrochemical reactions, and the influences of molar ratio of Fe/V on the structure and electrochemical properties of NGCs. This nanoscale design offers a new possibility improved the electrochemical performances of Li+/Na+ mixed-ion batteries (LNMIBs). The NGCs-3 electrode exhibits a higher discharge capacity (145 mAh g−1) and energy storage density (525 Whkg−1) at 5C, and the capacity retention reaches 70% after 1000 cycles. More importantly, we have established a direct relationship between the electrochemical kinetics and nanostructure of NGC electrode materials.