Silicon based composite electrodes for lithium ion batteries are of significant interest because of their potential to be high capacity alternatives to the commonly used graphitic carbon anodes. A drawback to their use, however, is the Si particle debonding and fracture that occurs as a result of the volumetric expansion by the lithium host particles upon lithiation of the anode electrode. We use X-ray micro computed tomography to visualize the evolution of the internal microstructure of a silicon-based electrode before and after four lithiation steps during the first half cycle of the cell. We develop a novel threshold edge detect method to perform 3D volumetric measurements of silicon particle expansion. According to our results, 100% lithiation of the composite anode resulted in up to 290% volume expansion of individual Si particles. Furthermore, the global and localized image intensity histogram profiles from 3D data were used to analyze the silicon particle X-ray attenuation effects as a function of lithiation: a decreasing attenuation with lithiation and the propagation of the reaction front through a core–shell process between the original state and 25% lithiation of the silicon-based electrode have been observed.