Composite separators of poly(vinylidene fluoride) (PVDF) with different contents of montmorillonite (MMT) for Li-ion batteries have been fabricated by electrospinning. The morphology, function group, crystallinity, and mechanical properties of membranes were investigated by scanning electron microscope (SEM), Fourier Transform infrared spectra (FT-IR), differential scanning calorimetry (DSC), and tensile test, respectively. Interlayer spacing of MMT in polymer was characterized by X-ray diffraction (XRD). In addition, the results of electrochemical measurements suggest that PVDF/MMT-5% composite membrane has maximum ionic conductivity of 4.2 mS cm(-1), minimum interfacial resistance of 97 Omega, and excellent electrochemical stability. The cell comprising PVDF/MMT-5% composite membrane shows higher capacity and more stable cycle performance than the one using commercial Celgard PP membrane. (C) 2016 Elsevier Ltd. All rights reserved.