In this study, the method of hydrothermal synthesis is introduced to prepare the titanium dioxide (i.e., TiO2) tetragonal prism array on the conducting plane of fluorine-doped tin oxide (i.e., FTO), and then the polyaniline (i.e., PANI) is coated on the surface of TiO2 array by normal chemical oxidation to form the PANI/TiO2 shell/core nanoarray. The array architecture of PANI/TiO2 composite is further confirmed by SEM, XPS, XRD, UV-vis and Raman spectroscopy. The regular array structure of PANI/TiO2 can reduce the resistance of ionic diffuse and charge transfer via optimizing the ionic diffusion to obtain a lower impedance and higher specific capacitance. Compared with the individual component (PANI or TiO2), the PANI/TiO2/FTO electrode possesses a higher specific capacitance as the supercapacitor electrode material. The maximum specific capacitances of 633 F/g at the rate of 10 mV/s and 781 F/g at the current density of 1 A/g are obtained in the PANI/TiO2/FTO electrode and it is superior or close to individual PANI or PANI-based materials. In addition, the TiO2 array can undertake some mechanical deformation in the redox process without destroying the electrode material to enhance the cyclic stability of PANI/TiO2/FTO electrode. The capacitance retention of PANI/TiO2/FTO electrode keeps 75% of its initial value which is higher than that of the PANI/FTO electrode (65%) after 2000 cycles. Therefore, such array architecture composite can be promisingly used as the electrode material for electrochemical capacitive energy storage. (C) 2019 Elsevier Ltd. All rights reserved.