Monocrystalline AlxGa1−xN(0001) (0.05 ≤ x ≤ 0.70) thin films, void of oriented domain structures and associated low-angle grain boundaries, have been grown at high temperatures via OMVPE directly on vicinal and on-axis α(6H)-SiC(0001) wafers using TEG, TEA and ammonia in a cold-wall, vertical, pancake-style reactor. The surface morphologies were smooth and die densities and distributions of dislocations were comparable to that observed in GaN(0001) films grown on high temperature A1N buffer layers. Double-crystal XRC measurements showed a FWHM value as low as 186 arc sec for the (0002) reflection. Spectra obtained via CL showed strong near band-edge emissions with FWHM values as low as 31 meV. The compositions of the AlxGa1−xN films were determined using EDX, AES and RBS and compared to the values of the bandgap as measured by spectral ellipsometry and CL emissions. A negative bowing parameter was found. Controlled n-type, Si-doping of AlxGa1−xN for x ≤ 0.4 has been achieved with net carrier concentrations ranging from ≈ 2 × 1017 cm−3 to 2 × 1019 cm−3. Acceptor doping with Mg for x < 0.13 was also successful.