This work deals with nitrogen-doped TiO₂ nanofibers with increased ionic conductivity and good catalytic activity, as a potential cathode catalyst for lithium–air battery. The electrochemical enhancement with nitrogen-doped TiO₂ in comparison with pristine TiO₂ could be realized by the changed electronic properties correlated with the evolution of oxygen vacancies altering the surface oxidation state of TiO₂. A discharge capacity greater than 11 000 mA h g⁻¹_(carbon) and a cyclic retention more than 25 cycles were achieved with the corresponding nitrogen-doped TiO₂ catalyst.