Ternary host–guest nanocomposite based on vanadium oxide and two polymers with different types of conductivity (ionic and electronic) – polypyrrole (PPy) and polyethylene oxide (PEO) – is prepared by solventless mechanochemical synthesis. The nanocomposite can be reversibly cycled with a specific capacity of ∼200mAhg−1 for at least one hundred cycles of full charge–discharge as the active component of the positive electrode of lithium batteries. Electrochemical performance of ternary PPy0.1PEO0.15V2O5 is compared with two-component analog PPy0.1V2O5. The presence of macromolecules of an ion-conducting polymer in the composition of the ternary nanocomposite PPy0.1PEO0.15V2O5 promotes interfacial transfer of lithium ions and also facilitates faster transport inside the particles of the nanocomposite.