PVdF-based separators are very promising materials in electrochemical energy storage systems but they suffer from fairly poor mechanical properties. To overcome this drawback, composite PVdF separators were fabricated and characterized in electrolytes of Li-ion batteries and supercapacitors. Macroporous PVdF composite separators were prepared by phase inversion method using PA and PET, and non-woven cellulose as support layers. Ionic conductivity and thermomechanical analyses were performed using electrolytes of Li-ion batteries and supercapacitors. The composite approach allowed a tremendous increase of the mechanical performances of the separator (between 340 and 750MPa) compared to the unreinforced PVdF separator (56MPa), without compromising the ionic conductivities (up to 15.6mScm−1).