Blue hydrogenated rutile TiO2 nanoparticles (blue TiO2) are prepared by treating white rutile via an enhanced hydrogenation process (i.e., high pressure and temperature). The materials characterization results demonstrate that the hydrogenation process leads to the increase in the unit cell volume and decrease in the size compared with the untreated white TiO2. The electrochemical impedance spectra analyses and theoretical energy calculations using density functional theory (DFT) suggest that the hydrogenation process not only improves electronic conductivity due to the formation of oxygen vacancy in the hydrogenation process but also dramatically augments lithium-ion mass transport within the crystalline lattice due to the introduction of oxygen vacancy and crystalline dislocation. Because of these characteristics resulting from the hydrogenation process, the blue TiO2 based lithium ion batteries (LIBs) possess significantly higher energy capacity and better rate performance than the white TiO2 based LIBs. In particular, at the rate of 0.1 and 5 C (1 C = 336 mAh g–1), the discharge capacities of the blue rutile are maintained at ca.179.8 and 129.2 mAh g–1, while the capacities of the white TiO2 are just ca. 119.6 and 55.5 mAh g–1, respectively.