Silicon carbide (SiC) nanowhiskers (NWs) constitute an important type of optical and structural materials. Herein, SiC NWs were successfully combustion synthesized (CSed) in a Si-C-N system using tungsten (W) as a catalyst. Scanning electron microscopy, transmission electron microscopy, and X-ray diffraction were used to characterize the SiC NWs. Results of morphological characterization indicated that the W-catalyzed CSed SiC NWs products were fluffy from surface to the core, and they were about several hundred micrometers in length with diameters less than 1 µm. For the comprehensive understanding of the initial growing progress of W-catalyzed CSed SiC NWs, the absorption behavior of C, N, and Si atoms on the crystal planes of W (100), W (110), and W (111) surfaces was investigated by using first-principles calculations. The calculated surface energy (E surf ) of the studied W surfaces and the absorption energy of C, N, and Si atoms on different sites, indicate that the C atom has a priority to sink to the nanometer catalysts grain of W, and the pre-sunk C atom then reacts with Si atom to form NWs.