Silicon is a promising material for negative electrode in Li-ion batteries because of high gravimetric capacity. A Si nanomaterial that can accommodate volume expansion accompanied by lithiation is needed for practical application in Li-ion batteries. We prepare three-dimensional nanoporous interconnected silicon material with controlled pore and ligament sizes by dealloying using an Mg-Si precursor and Bi melt. The Mg atoms in the precursor selectively dissolve into Bi, and the remaining Si atoms self-organize into a nanoporous structure with characteristic length ranging from several ten to hundred nanometer. The Li-ion battery electrodes made from nanoporous silicon exhibit higher capacities, increased cycle lives, and improved rate performances compared with those made from commercial Si nanoparticles. Measurements on the electrical resistivity and electrode thickness change by lithiation/delithiation suggest that the superior performance of nanoporous Si electrode originates from the following: (1) The nanoporous Si has much lower electrical resistivity compared with that of the nanoparticle Si owing to the n-type dopant incorporated during dealloying. (2) The nanoporous Si-based electrode has higher porosity owing to the presence of intra-particle pores, which can accommodate Si expansion up to higher levels of lithiation. (C) 2015 Elsevier B.V. All rights reserved.