An effective and practical method for producing Si/C composites with 10–15wt% of silicon nanoparticles embedded in a carbon matrix is developed. The procedure consists of mechanically mixing Si with pitch followed by dispersing in toluene and final heat-treatment between 1000 and 1100°C. The homogeneity of the materials was confirmed by optical microscopy and HRTEM. X-ray photoelectron spectroscopy, X-ray diffraction and N2 adsorption at 77K were applied for determining the structural and textural characteristics. The lithium insertion/deinsertion performance was monitored from the galvanostatic charge–discharge characteristics using a Si/C–lithium two-electrode cell, and varying the electrochemical parameters. Silicon essentially enhances the electrode capacity (C rev up to 600mAh/g for 15% Si), the effect being proportional to the component content, but it affects the cycle life. The first cycle reversible capacity increases with the decrease of current density and discharge cut-off potential. However, using such conditions during cycling leads to rapid saturation of the silicon particles, from which the decay of the electrochemical performance starts. It is demonstrated that the evolution of reversible and irreversible capacity is strongly dependent on the kinetics of lithium diffusion in silicon particles and on the discharge potential cut-off.