Highly porous Si/TiO2 composite nanofibres were prepared using a unique sulphur-templating method combined with electrospinning. The structure, morphology, surface area, phase and composition of these nanofibres were characterized using Raman spectroscopy, scanning electron microscopy, powder X-ray diffraction, surface area analyser and thermogravimetric analyser. The specific surface area of Si/TiO2 porous NFs is as large as 387 m2 g−1, whose silicon capacity can be maintained above 1580 mAh g−1 in 180 cycles.