We demonstrate that electrospray could be combined with a sol-gel process to produce non-spherical nanostructures. The electrosprayed nanodroplets solidified under Rayleigh instability via a controlled sol-gel reaction, enabling us to capture elongated intermediates in the solid form. This work demonstrates the potential of electrospray, a remarkably simple and well-established technique, for fabricating one-dimensional nanostructures by taking advantage of the Rayleigh instability phenomenon. It also provides direct experimental evidence to confirm the existence of Rayleigh instability for electrified nanodroplets. (C) 2007 Elsevier B.V. All rights reserved.