Highly pure Al₄SiC₄ powders were prepared by carbothermic reduction at 2173 K using Al₂O₃, SiO₂, and graphite as raw materials. The obtained Al₄SiC₄ powders owned hexagonal plate-like grains with a diameter of about 200–300 μm and a thickness of about 2–6 μm. Based on the experimental results, the reaction of Al₄SiC₄ formation and grain evolution mechanisms were determined from thermodynamic and first-principles calculations. The results indicated that the synthesis of Al₄SiC₄ by the carbothermic reduction consisted of two parts, i.e., solid–solid reactions initially followed by complex gas–solid and gas–gas reactions. The grain growth mechanism of Al₄SiC₄ featured a two-dimensional nucleation and growth mechanism. The gas phases formed during the sintering process favored the preferential grain growth of (0010) and (1 ī0) planes resulting in formation of hexagonal plate-like Al₄SiC₄ grains.