Well-dispersed TiO2/ZrO2 nanofibers-doped activated carbon (AC/TiZr) were successfully synthesized as an electrode for the capacitive deionization (CDI) technique via electrospinning that was followed by a hydrothermal treatment. SEM, TEM, XRD, XPS and EDX measurements were employed to characterize the morphology, crystal structure and chemistry composition of the as-synthesized material. The electrochemical performance of the AC/TiZr nanocomposite modified electrode was measured using systematic cyclic voltammetry (CV) experiments. The highest specific capacitance for the AC/TiZr-based electrode is 251.3 Fg/g, which is higher than those of the AC (207.4 Fg/g) and TiO2/ZrO2 NFs (0.4 Fg/g)-based electrodes, and the interior resistance was also reduced. A desalination performance enhancement was obtained in the case of the AC/TiZr and the electrosorptive is 2.96 mg g−1. The implementation of the AC/TiZr nanocomposite provided a high potential for improving the efficiency of CDI.