The synthesis of Si nanoparticles by ultrasonication processing of porous Si powder and a novel method for preparing a high-capacity Si/C composite using this technique is reported. The porous Si powder is prepared by selectively etching the silicide phase of a Ti24Si76 alloy consisting of Si and silicide phases. The particle size of the nanocrystalline Si is determined by the crystallite size of the Si and silicide phases in the alloy powder. Ultrasonication of the porous Si obtained from the mechanically alloyed Ti24Si76 alloy generates nanocrystalline Si particles of size about 5nm. Growth of the Si and silicide phases in the alloy is induced by annealing of the mechanically alloyed sample, with a consequent increase in the size of the Si particles obtained after ultrasonication. Application of the ultrasonication process to the fabrication of Si/C composite anode materials generates nanometer-scale Si particles in situ that are distributed in the matrix. Analysis of the phases obtained and evaluation of the distribution of the nanometer-scale Si particles in the composites via XRD/TEM measurements show that the nanometer-scale Si particles are effectively synthesized and uniformly distributed in the carbon matrix, leading to enhanced electrochemical performance of the Si/C composites.