A series of Si/C composites were fabricated based on pitch and Si powders with particle sizes of 30, 100, 500, and 3000 nm. The size effects of the Si particles in the Si/C composites were investigated for lithium-ion battery anodes. The nanoscale Si and Si/C composites exhibited good capacity retentions. Scanning electron microscopy showed that exterior and interior cracks emerging owing to volume expansion as well as parasitic reactions with the electrolyte could well explain the performance failure.