Herein, ZrSiO4/B2O3/Mg/C system was used to synthesize a ZrB2-based composite by means of a high energy ball milling process. A mechanically induced self-sustaining reaction was achieved in this system. A nanocomposite powder of ZrB2–SiC–ZrC was prepared with an ignition time of approximately 6 min of milling. The role of the stoichiometric amounts of B2O3 and carbon was investigated to clarify the governing mechanism for the formation of the product.