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Silicon carbide (SiC) whiskers were synthesized from SiO2-CH4-Na3AlF6 system. The whiskers obtained were cylindrical in shape, and they had uniform diameter (0.1–5.0 μm) and length (50 μm-10 mm). They were found to have grown by a Vapor-Liquid-Solid (VLS) mechanism since a catalyst droplet was observed on the tip of most of the whiskers. The composition of the Al-Si droplets was determined by means of EDAX. As no researchers have previously reported on Al-Si droplets, we conducted a detailed analysis of them in this study.