A novel CNT-TiO2 film was prepared by electrochemical deposition of TiO2 nanostructures on the CNT film. The ion transfer kinetics of three-dimensional rutile were dominated by ion adsorption. Display omitted •A three-dimensional TiO2 structure on CNT film was successfully created.•This unique TiO2 nanostructure exhibits outstanding activity and stability.•Significantly, the optimized TiO2-CNT composite delivers high energy density, power density, and excellent cycle life. Developing high capacity solid-state super capacitors and exploring their storage mechanism is one of the ongoing scientific topics. Here a novel TiO2-carbon nanotube (CNT) electrode is prepared by electrochemical deposition of TiO2 nanostructures on the CNT film. In situ Raman spectroscopy showed that the ion transfer kinetics of 3D rutile-based TiO2 were mainly controlled by ion adsorption. Symmetric solid-state supercapacitors compose of two TiO2-CNT electrodes and H2SO4-polyvinyl alcohol gel electrolyte. The devices show a high energy density of 82.5 Wh kg−1 and specific capacitance of 345.7F g−1 at 1.0 A g−1. Furthermore, the TiO2-CNT supercapacitor illustrates excellent cyclic stability with capacitor retention of 93.3% after 10,000 cycles, and a low leakage current of 9 μA after 2 h. This may due to the matching of the diffusion path topology of the rutile-doped less anatase structure. These results demonstrate that the TiO2-CNT supercapacitor may bring new opportunities to the power supply of portable electronics in the future.