Poly(vinylidene fluoride) (PVDF) and its copolymer have been widely studied for applications in rechargeable batteries [1]. It has been reported that increasing the pore size (e.g. to micron size) in the PVDF matrix can help to enhance the ionic conductivity and thus improve cell rate capability. Polymer electrolytes have been obtained both by the standard cast- ing procedure [2,3], and by the absorption/extraction method [4]. On the other hand, casting technology is discouraged for large-scale applications, whereas the preparation by extrac- tion of dibutylphthalate leads to porosities not higher than 50% in volume.