Recently, hybrid capacitive deionization devices have gathered much attention due to high ion removal capacity, rapid ion capture and excellent stability. In this study, sodium ion battery material-reduced graphene oxide/cobalt oxide (rGO/Co3O4) has been successfully synthesized and investigated as a potential cathode for hybrid capacitive deionization (HCDI) systems for the first time. The structure and morphology of rGO and rGO/Co3O4 composites have been analyzed using XRD, FT-IR, TGA and SEM. The characterization confirms the homogeneous crystal growth of Co3O4 on the rGO sheets, with rGO weight % of 9.4 (rGO/Co3O4-A) and 25.2 (rGO/Co3O4-B). The cyclic voltammetry studies indicated that the rGO/Co3O4-B electrode exhibited high specific capacitance (210 F g−1 at 5 mV s−1) with redox properties. This paper also investigates the influence of initial concentration and voltage on the ion removal capacity of the rGO and rGO/Co3O4 composites. The rGO/Co3O4-B based HCDI system presents a significantly high ion removal capacity of 18.63 mg g−1 (250 mg L−1, 1.6 V), which is 2.8 times higher than pure rGO based CDI system (6.45 mg g−1). Also, the rGO/Co3O4 composites exhibited excellent regeneration ability indicating its potential use in high performance CDI systems. © 2018 Elsevier B.V.