Capacitive Deionization (CDI) is an emerging technology with great potential applications. Most researchers view it as a viable water treatment alternative to reverse osmosis. This research reports the preparation and application of a carbon aerogel polypyrrole (CA-PPy) composite for the desalination of NaCl solution by the hybrid CDI method. The carbon aerogel (CA) was prepared from a Resorcinol / Formaldehyde precursor by the sol–gel method. The aerogel obtained from the sol–gel was then pyrolysed in a tube furnace to form CA. Polypyrrole (PPy) was prepared by the Oxidative chemical polymerisation of pyrrole, ferric chloride hexahydrate (oxidant), and sodium dodecyl sulfate (dopant). A composite of CA and PPy was then prepared and used to modify carbon electrodes. The CA-PPy composite was characterised to verify its composition, morphology, thermal properties, and functional groups. The electrochemical properties of the material were determined by Cyclic voltammetry (CV) and Electrochemical impedance spectroscopy (EIS) tests. The electrochemical tests were done using a GAMRY potentiostat electrochemical workstation, a 1.0 M KCl was used as the electrolyte, and the applied potential window was (-0.2 to + 0.6) V for the CV test. The EIS test was done with the same concentration of KCl electrolyte at an applied potential of 0.22 V and at a frequency range of (0.1 – 100, 000) Hz. The optimal specific capacitance of the CA is 115F/g, and that of the composite is 360.1F/g, they were both obtained at a scan rate of 5 mV/s. The CDI desalination study of the CA-PPy composite showed a salt adsorption capacity (SAC) of 10.10 mg/g (300 mg/L NaCl solution) – 15.7 mg/g (800 mg/L NaCl solution) at 1.2 V applied voltage. The salt recovery efficiency of the electrode material in the 300 mg/L solution is 27 %, in the 500 mg/L solution, it is 20.12 %, and in the 800 mg/L solution, it is 15.41 %. The electrode material also showed good electrochemical stability after nine cycles of ion adsorption/desorption study.