A third generation mist chemical vapor deposition (3rd G mist CVD) system was used to grow six single-layer and two heterostructure α-(AlxGa1−x)2O3 buffers on c-plane sapphire substrates for the subsequent deposition of conductive Sn-doped α-Ga2O3 (Sn:α-Ga2O3) thin films. In the six single-layer buffers, the Al contents x increased from 0 to 0.66. The two heterostructure buffers consisted of six ∼20-nm- and ∼100-nm-thick layers laying on top of each other. The 3rd G mist CVD system enabled the growth of these complicated multi-layer heterostructures in a single run, while mono-crystallinity was still maintained in all grown layers. Strain was observed in the 20-nm heterostructure, while the layers in the 100-nm heterostructure almost fully relaxed and the Vegard’s law was followed even when the α-(AlxGa1−x)2O3 layers were stacked on each other. Transmission electron microscopy analyses show that the dislocation densities remained high in the order of 1010 cm−2 despite the employment of the buffers. PtOx and AgOx Schottky diodes (SDs) were fabricated on the Sn:α-Ga2O3 films. The barrier height vs ideality factor plots could be fitted by linear dependences, indicating that the large ideality factors observed in α-Ga2O3 SDs could be explained by the inhomogeneity of the SDs. The extrapolation of the dependences for the PtOx and AgOx SDs yielded homogeneous Schottky barrier heights of ∼1.60 eV and 1.62 eV, respectively, suggesting that the Fermi level was pinned at the Ec − 1.6 eV level. The Sn:α-Ga2O3 film grown on the strained 20-nm heterostructure buffer showed best characteristics overall.