As potential high-performance anodes for Li-ion batteries (LIBs), hierarchical heteronanostructures consisting of TiNb2O7 nanofibers and ultrathin MoS2 nanosheets (TNO@MS HRs) were synthesized by simple electrospinning/hydrothermal processes. With their growth mechanism revealed, the TNO@MS HRs exhibited an entangled structure both for their ionic and electronic conducting pathways, which enabled the synergetic combination of one-and two-dimensional structures to be realized. In the potential range of 0.001-3 V vs Li/Li+, the TNO@MS HR-based LIBs exhibited high capacities of 872 and 740 mAh g(-1) after 42 and 200 cycles at a current density of 1 A g(-1), respectively, and excellent rate performance of 611 mAh g(-1) at 4 A g(-1). We believe that the fabrication route of TNO@MS HRs will find visibility for the use of anode electrodes for high capacity LIBs at low cost.