We introduce membrane pseudocapacitive deionization (MPDI) of a hybrid cell consisting of one electrode of hydrated vanadium pentoxide (hV2O5) decorated on multi-walled carbon nanotubes electrode (MWCNT) and one electrode of activated carbon. This hybrid system enables sodium removal by pseudocapacitive intercalation to MWCNT-hV2O5 electrode and chloride removal by non-Faradaic electrosorption of the porous carbon electrode. MWCNT-hV2O5 electrode was synthesized by electrochemical deposition of hydrated vanadium pentoxide on the MWCNT paper. The stable electrochemical operating window for MWCNT-hV2O5 electrode is identified between -0.5 V and +0.4 V vs. Ag/Cl which provides a specific capacity of 44 mAh/g (corresponds with 244 F/g) in aqueous 1 M NaCl. The desalination performance of the MPDI system was investigated in aqueous 200 mM NaCl (brackish water) and 600 mM NaCl (sea water) solutions. With the aid of an anion and a cation exchange membrane, the MPDI hybrid cell was operated from -0.4 V to +0.8 V cell voltage without crossing the reduction and oxidation potential limit of both electrodes. For the 600 mM NaCl solution, the NaCl salt adsorption capacity of the cell was 23.6±2.2 mg/g which is equivalent to 35.7±3.3 mg/g as normalized to the mass of the MWCNT-hV2O5 electrode. Additionally, we propose a normalization method for the electrode material with Faradaic reactions based on sodium uptake capacities.