A set of two-component guest–host nanocomposites composed of conducting polymers and vanadium oxide are prepared via a single-step, solvent-free synthesis. The composition, structure, physical and electrochemical properties of these materials are studied. The nanocomposites have a guest–host structure, with the conducting polymer located in the interlayer space of the inorganic nanoparticles. The nanocomposites are capable of reversible cycling as the positive electrode in a lithium ion cell, and retain their capacity over one hundred full charge–discharge cycles. After cycling at a current of ∼0.2Ag−1, their capacity is restored when cycling at lower current, demonstrating the stability of their structure.