A porous V 2 O 5 lump with a very large surface area could be prepared by removal of B 2 O 3 from a melt quenched V 2 O 5 -B 2 O 3 binary mixture of 4:1 molar ratio. The surface area reached 34.75 m 2 g - 1 and a very interesting gathering texture of V 2 O 5 tiny needle crystals was observed with a lot of vacant space for electrolyte solvent to soak in. A lithium rechargeable cell using the porous V 2 O 5 showed superior electrochemical performances with current drain ~400 μAcm - 2 and discharge capacity ~114 mAhrg - 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 V 2 O 5 samples were used. A porous sample was discharged to around x=0.8 in Li x V 2 O 5 through α- to -phases and cycled in the latter range.