Silicon anodes have attracted considerable attention for their use in lithium-ion batteries because of their extremely high theoretical capacity; however, they are prone to extensive volume expansion during lithiation, which causes disintegration and poor cycling stability. In this article, we use two approaches to address this issue, by reducing the size of the Si particles to nanoscale and incorporating them into a carbon composite to help modulate the volume expansion problems. We improve our previous work on the solution-plasma-mediated synthesis of Si nanoparticles (NPs) by adjusting the electrolyte medium to mild buffer solutions rather than strong acids, successfully generating Si-NPs with <10 nm diameters. We then combined these Si-NPs with carbon using MgO-template-assisted sol-gel combustion synthesis, which afforded porous carbon composite materials. Among the preparations, the composite material obtained from the LiCl 0.2 M + H3BO3 0.15 M solution-based Si-NPs exhibited a high reversible capacity of 537 mAh/g after 30 discharge/charge cycles at a current rate of 0.5 A/g. We attribute this increased reversible capacity to the decreased particle size of the Si-NPs. These results clearly show the applicability of this facile and environmentally friendly solution-plasma technique for producing Si-NPs as an anode material for lithium-ion batteries.