Two dimensional (2D) transition metal oxides and chalcogenides demonstrate a promising performance in sodium-ion batteries (SIBs) application. In this study, we investigated the use of a composite of freeze dried V2O5·nH2O nanosheets and multi-walled carbon nanotube (MWCNT) as a negative electrode material for SIBs. Cyclic voltammetry (CV) results indicated that a reversible sodium-ion insertion/deinsertion into the composite electrode can be obtained in the potential window of 0.1–2.5 V vs. Na+/Na. The composite electrodes delivered sodium storage capacities of 140 and 45 mAh g−1 under applied current densities of 20 and 100 mA g−1, respectively. The pause test during constant current measurement showed a raise in the open circuit potential (OCP) of about 0.46 V, and a charge capacity loss of ∼10%. These values are comparable with those reported for hard carbon electrodes. For comparison, electrodes of freeze dried V2O5·nH2O nanosheets were prepared and tested for SIBs application. The results showed that the MWCNT plays a significant role in the electrochemical performance of the composite material.