We report the preparation and characterization of amorphous silicon–carbon (Si–C) nanospheres as anode materials in Li-ion batteries. These nanospheres were synthesized by a chemical vapor deposition at 900 °C using methyltrichlorosilane (CH3SiCl3) as both the Si and C precursor, which is a cheap byproduct in the organosilane industry. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, nitrogen adsorption, thermal gravimetric analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy. It was found that the synthesized Si–C nanospheres composed of amorphous C (about 60 wt%) and Si (about 40 wt%) had a diameter of 400–600 nm and a surface area of 43.8 m2 g−1. Their charge capacities were 483.6, 331.7, 298.6, 180.6, and 344.2 mA h g−1 at 50, 200, 500, 1000, and 50 mA g−1 after 50 cycles, higher than that of the commercial graphite anode. The Si–C amorphous structure could absorb a large volume change of Si during Li insertion and extraction reactions and hinder the cracking or crumbling of the electrode, thus resulting in the improved reversible capacity and cycling stability. The work opens a new way to fabricate low cost Si–C anode materials for Li-ion batteries.