Carbon nanofibers (CNFs) have been successfully prepared by using electrospinning at various flowrates, and were formed from polyvinyl alcohol (PVA) and activated carbon (700-1400 m2/g) as electrodes on capacitive deionization. Before being furthermore deposited into electrodes, characterization was carried out on CNFs by using SEM. Cyclic voltammetry analysis was also performed to determine the electrolysis mechanism of the electrodes. The best results in removing salt reaching 70% were achieved by capacitive deionization systems with the smallest diameter size of CNFs, at a voltage of 1.5 V. The CNFs formed by electrospinning have potential to be used as excellent capacitive deionization electrodes for the desalination process.