Capacitive deionization (CDI) has garnered significant interest for desalinating water and wastewater. However, electrode materials have remained a primary constraint in CDI technology. This study incorporated carbon nanotubes (CNTs) into a polyacrylonitrile (PAN) solution to synthesize a hierarchically porous activated carbon nanofiber (ACNF)/CNT composite. The ACNF/CNT composite possesses a highly flexible structure characterized by a distinctive beads-on-string morphology. It exhibits a specific surface area of 699 m2/g, a specific pore volume of 0.448 cm3/g, and an average pore width of 3.38 nm. The composite is composed of micropores (38 %), mesopores (59 %), and macropores, creating a multi-scale porous architecture. The surface capacitance of the ACNF/CNT composite is six times greater than that of the ACNF alone, and its charge transfer resistance is reduced to one-tenth. Furthermore, the electrosorption capacity of the ACNF/CNT composite as CDI electrodes was found to be 17.3 mg/g for a 500 mg/L NaCl solution, demonstrating stability over 30 cycles. Kinetic studies suggest that the mesopore-rich beads-on-string structure enhances intraparticle diffusion and the electrosorption process. The ACNF/CNT composite also demonstrates exceptional flexibility and mechanical stability, which are crucial for its application at a pilot scale. This study introduces a novel hierarchically porous electrode material for CDI desalination.