Si–TiN alloys were prepared by reactive gas mechanical milling of Si and Ti powders in N2(g) for use as anode materials in Li-ion cells. This is a low-cost and simple method to prepare Si–TiN anode materials. As a comparison, Si–TiN alloys were also synthesized more conventionally by ball milling Si and TiN powders in Ar. Both Si–TiN alloys have similar phase compositions, however the Si–TiN alloys prepared by N2 reactive gas milling have a more homogenous TiN distribution at the nanometer-scale. As a consequence, Si–TiN alloys prepared by N2 reactive gas milling where much more resistant to Li15Si4 formation during cycling in Li-cells, resulting in improved cell performance.