Li4Ti4.95V0.05O12 and Li4Ti5O12 powders were successfully prepared by a solid-state method. XRD reveals that both samples have high phase purity. Raman spectroscopy indicates that the Ti–O vibration have a blue shift. SEM shows that Li4Ti4.95V0.05O12 has a slightly smaller particle size and a more regular morphological structure with narrow size distribution than those of Li4Ti5O12. Galvanostatic charge–discharge testing indicates both samples have nearly equal initial capacities at different discharge voltage ranges (0–2 and 0.5–2V), but Li4Ti4.95V0.05O12 has a higher cycling performance than that of Li4Ti5O12. CV suggests that Li4Ti4.95V0.05O12 has lower electrode polarization and high lithium ion diffusivity in solid-state body of sample, implying that the vanadium doping is beneficial to the reversible intercalation and de-intercalation of Li+. The novel Li4Ti4.95V0.05O12 materials may find promising applications in lithium ion batteries and electrochemical cells due to the excellent electrochemical performace and simple synthesis route.