Na-ion capacitors have attracted extensive interest due to the combination of the merits of high energy density of batteries and high power density as well as long cycle life of capacitors. Here, a novel Na-ion capacitor, utilizing TiO2@CNT@C nanorods as an intercalation-type anode and biomass-derived carbon with high surface area as an ion adsorption cathode in an organic electrolyte, is reported. The advanced architecture of TiO2@CNT@C nanorods, prepared by electrospinning method, demonstrates excellent cyclic stability and outstanding rate capability in half cells. The contribution of extrinsic pseudocapacitance affects the rate capability to a large extent, which is identified by kinetics analysis. A key finding is that ion/electron transfer dynamics of TiO2@CNT@C could be effectively enhanced due to the addition of multiwalled carbon nanotubes. Also, the biomass-derived carbon with high surface area displays high specific capacity and excellent rate capability. Owing to the merits of structures and excellent performances of both anode and cathode materials, the assembled Na-ion capacitors provide an exceptionally high energy density (81.2 W h kg−1) and high power density (12 400 W kg−1) within 1.0–4.0 V. Meanwhile, the Na-ion capacitors achieve 85.3% capacity retention after 5000 cycles tested at 1 A g−1.