Capacitive deionization is a second-generation water desalination technology in which porous electrodes (activated carbon materials) are used to temporarily store ions. In this technology, porous carbon used as electrodes have inherent limitations, such as low electrical conductivity, low capacitance, etc., and, as such, optimization of electrode materials by rational design to obtain hybrid electrodes is key towards improvement in desalination performance. In this work, different compositions of mixture of reduced graphene oxide (RGO) and activated carbon (from 5 to 20 wt% RGO) have been prepared and tested as electrodes for brackish water desalination. The physico-chemical and electrochemical properties of the activated carbon (AC), reduced graphene oxide (RGO), and as-prepared electrodes (AC/RGO-x) were characterized by low-temperature nitrogen adsorption measurement, scanning electron microscope (SEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier transform infra-red (FT-IR), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). Among all the composite electrodes, AC/RGO-5 (RGO at 5 wt%) possessed the highest specific capacitance (74 F g−1) and the highest maximum salt adsorption capacity (mSAC) of 8.10 mg g−1 at an operating voltage ∆E = 1.4 V. This shows that this simple approach could offer a potential way of fabricating electrodes of accentuated carbon network of an improved electronic conductivity that’s much coveted in CDI technology.