TiO2-doped activated carbon fibers (ACFs) were successfully prepared as capacitive deionization (CDI) electrode materials by facile ultrasonication-assisted process. ACFs were treated with titanium isopropoxide (TTIP) and isopropyl alcohol solutions of different concentrations and then calcinated by ultrasonication without heat-treatment. The results show that a certain amount of anatase TiO2 was present on the ACF surface. The specific capacitance of the TiO2-doped ACF electrode was remarkably improved (by 93.8% at scan rate of 50 mV s–1) over that of the untreated ACF electrode, despite decreases in the specific surface area and total pore volume upon TiO2 doping. From the CDI experiments, the salt adsorption capacity and charge efficiency of the sample with TTIP percent concentration of 15% were found to considerably increase by 71.9 and 57.1%, respectively. These increases are attributed to the improved wettability of the electrode, which increases the number of surface active sites and facilitates salt ion diffusion in the ACF pores. Additionally, the Ti-OH groups of TiO2 act as electrosorption sites, which increases the electrosorption capacity.