We report on the electrochemical performance of V2O3 polycrystalline nanorods (poly-NRs) as a cathode material for Li-ion batteries. Poly-NRs are formed through the thermal treatment of V2O5 nanotubes in a N2 atmosphere. X-ray and electron diffraction techniques are used to confirm the thermal reduction. Through galvanostatic cycling, we demonstrate that poly-NRs offer excellent capacity retention over 750 cycles. The capacity retention from the 50th to the 750th cycle was an impressive 94 %, retaining a capacity of approximately 120 mAh g−1 after 750 cycles. The outstanding stability of the nanocrystal-containing V2O3 poly-NRs over many cycles demonstrates that vanadium(III) oxide (V2O3) performs very well as a cathode material. Full Li-ion cells with paired a V2O3 poly-NR cathode and a pre-charged Co3O4 inverse opal (IO) conversion mode anode demonstrated high initial capacities and retained a capacity of 153 mAh g−1 after 50 cycles. The capacities achieved with our V2O3 poly-NRs/Co3O4 IO full cells are comparable to the capacities obtained from the most commonly used cathode materials when cycled in a half-cell arrangement versus pure Li metal.