Anatase TiO2 nanopores are successfully prepared through alternating voltage induced electrochemical synthesis (AVIES) approach at room temperature. When utilizing TiO2 nanoporous materials as an anode for Na-ion battery, it delivers a reversible charge-discharge capacity of around 180 mA h g−1 at 0.2 C (67 mA g−1) after 200 cycles. Meanwhile, it also shows a good cycling performance and a high rate capability due to unique nanoporous structures, which promote electrolyte wetting and facilitate diffusion of Na+. Additionally, cyclic voltammetry demonstrate that the sodium-ion storage of as-prepared TiO2 is a cooperative control behavior of diffusion and capacitance, but mainly controlled by capacitive behavior, which further facilitates a rapid (de-)intercalation of Na+.