A porous V2O5 lump with a very large surface area could be prepared by removal of B2O3 from a melt quenched V2O5-B2O3 binary mixture of 4:1 molar ratio. The surface area reached 34.75 m(2) g(-1) and a very interesting gathering texture of V2O5 tiny needle crystals was observed with a lot of vacant space for electrolyte solvent to soak in. A lithium rechargeable cell using the porous V2O5 showed superior electrochemical performances with current drain similar to 400 mu A cm(-2) and discharge capacity similar to 114 mA hr g(-1). Several cycles were carried out between 2 to 4 V Limits using the porous samples. However this was not possible when commercially available and only melt quenched V2O5 samples were used. A porous sample was discharged to around x = 0.8 in LixV2O5 through alpha-to epsilon-phases and cycled in the latter range.