Mesostructured niobium (Nb)-doped TiO2-carbon (Nb-TiO2-C) composites are synthesized by a hydrothermal process for application as anode materials in Li-ion batteries. The composites have a hierarchical porous structure with the Nb-TiO2 nanoparticles homogenously distributed throughout the porous carbon matrix. The Nb content is controlled (0–10 wt%) to investigate its effect on the physico-chemical properties and electrochemical performance of the composite. While the crystalline/surface structure varied with the addition of Nb (d-spacing of TiO2: 0.34–0.36 nm), the morphology of the composite remained unaffected. The electrochemical performance (cycle stability and rate capability) of the Nb-TiO2-C composite anode with 1 wt% Nb doping improved significantly. First, a full cut-off potential (0–2.5 V vs. Li/Li+) of Nb-doped composite anode (1 wt%) provides a higher energy utilization than that of the un-doped TiO2-C anode. Second, Nb-TiO2-C composite anode (1 wt%) exhibits an excellent long-term cycle stability (100% capacity retention, 297 mAh/g at 0.5 C after 100 cycles and 221 mAh/g at 2 C after 500 cycles) and improved rate-capability (192 mAh/g at 5 C), respectively (1 C: 150 mA/g). The superior electrochemical performance of Nb-TiO2-C (1 wt%) could be attributed to the synergistic effect of improved electronic conductivity induced by optimal Nb doping (1 wt%) and lithium-ion penetration (high diffusion kinetics) through unique pore structures.