Composites of metal oxide with nanostructured carbons have been pursued intensively to evade issues like low intrinsic electronic conductivity, large irreversible capacity loss (IC), and poor coulombic efficiency (CE) of metal oxides in lithium-ion batteries (LIBs). In this report, we demonstrate one-pot solvothermal synthesis of V2O5 sheets using ethylene glycol and their composite with MWCNT by electrostatic self-assembly. The phase identification and morphological features were evaluated by XRD, FESEM, and HRTEM techniques, whereas structural properties were acquired from FTIR and Raman spectroscopy data. HRTEM of pristine V2O5 clearly confirms the formation of sheet-like morphology with few tens of nanometers thickness. Investigation of both the pristine V2O5 and V2O5/MWCNT composite materials as positive electrode in LIBs, the latter delivers a capacity of 265 mAh g(-1) at 0.1C and 180 mAh g(-1) at 1C rate which are higher than the performance of former (238 mAh g(-1) at 0.1C rate). The improved electrochemical performance of the V2O5/MWCNT composite cathode in terms of specific capacity, coulombic efficiency, and cycle life stability is ascribed to good electronic and ionic conductivity as well as high lithium storage along both sides of basal plane of V2O5 sheets.