The phase pure spinel lithium titanate (Li4Ti5O12) in the form of ultrafine fibre was synthesised by the combination of sol-gel and electrospinning techniques. The electrospinning process for the preparation of Li4Ti5O12 precursor was optimised to get bead-free fibrous mat with uniform thickness. Crystalline Li4Ti5O12 in the form of ultrafine fibre was synthesised by the calcination of the precursor at 800 A degrees C in air for 4 h. The material was characterised by X-ray diffraction, Raman spectroscopy and scanning electron microscopy and subsequently evaluated as an electrode active material using Li metal as a counter electrode. The material exhibited a first cycle specific capacity of 154 mAh g(-1) with good rate capability and cyclability.