SiC is a rapidly developing semiconductor suitable for high temperature, high frequency, and high power electronics. In this work, AlN coated sapphire (0001) has been developed as a new substrate for SiC thin film epitaxy. By predepositing a thin AlN buffer layer, the nucleation and adherence of the SiC film are vastly improved X-ray diffraction and electron channeling patterns have confirmed that single-crystal 6H-SiC was obtained on AlN/Al2O3 substrates. The undoped SiC film showed n-type electrical conductivity. The strain in the epilayer is small and the dislocation density is comparable to that in SiC grown on Si(111).