Monocrystalline GaN(0001) thin films have been grown at 950 °C on high-temperature, ≈ 100 nm thick, monocrystalline AlN(0001) buffer layers predeposited at 1100 °C on α(6H)−SiC(0001)Si substrates via OMVPE in a cold-wall, vertical, pancake-style reactor. These films were free of low-angle grain boundaries and the associated oriented domain microstructure. The PL spectra of the GaN films deposited on both vicinal and on-axis substrates revealed strong bound excitonic emission with a FWHM value of 4 meV. The near band-edge emission from films on the vicinal substrates was shifted slightly to a lower energy, indicative of films containing residual tensile stresses. A peak attributed to free excitonic emission was also clearly observed in the on-axis spectrum. Undoped films were too resistive for accurate Hall-effect measurements. Controlled n-type, Si-doping in GaN was achieved for net carrier concentrations ranging from approximately 1 × 1017 cm−3 to 1 × 1020 cm−3. Mg-doped, p-type GaN was achieved with nA−nD ≈ 3 × 1017 cm−3, ρ ≈ 7 Ω · cm, and μ ≈ 3 cm2/V · s. Double-crystal x-ray rocking curve measurements for simultaneously deposited 1.4 μm GaN films revealed FWHM values of 58 and 151 arcsec for deposition on on-axis and off-axis 6H−SiC(0001)Si substrates, respectively. The corresponding FWHM values for the AlN buffer layers were approximately 200 and 400 arcsec, respectively.