AlN-SiC alloy crystals, with a thickness greater than 500 µm, were grown on 4H- and 6H-SiC substrates from a mixture of AlN and SiC powders by the sublimation-recondensation method at 1860-1990 °C. On-axis SiC substrates produced a rough surface covered with hexagonal grains, while 6H- and 4H- off-axis SiC substrates with different miscut angles (8° or 3.68°) formed a relatively smooth surface with terraces and steps. The substrate misorientation ensured that the AlN-SiC alloy crystals grew two dimensionally as identified by scanning electron microscopy (SEM). X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed that the AlN-SiC alloys had the wurtzite structure. Electron probe microanalysis (EPMA) and x-ray photoelectron spectroscopy (XPS) demonstrated that the resultant alloy crystals had non-stoichiometric ratios of Al:N and Si:C and a uniform composition throughout the alloy crystal from the interface to the surface. The composition ratio of Al:Si of the alloy crystals changed with the growth temperature, and differed from the original source composition, which was consistent with the results predicted by thermodynamic calculation of the solid-vapor distribution of each element. XPS detected the bonding between Si-C, Si-N, Si-O for the Si 2p spectra. The dislocation density decreased with the growth, which was lower than 106 cm−2 at the alloy surface, more than two orders of magnitude lower compared to regions close to the crystal/substrate interface, as determined by TEM.