We present a systematic study on the influence of the miscut orientation on structural and electronic properties in the homoepitaxial growth on off-oriented β-Ga 2 O 3 (100) substrates by metalorganic chemical vapour phase epitaxy. Layers grown on (100) substrates with 6° miscut toward the  direction show high electron mobilities of about 90 cm 2 V -1 s -1 at electron concentrations in the range of 1-2 × 10 18 cm -3 , while layers grown under identical conditions but with 6° miscut toward the  direction exhibit low electron mobilities of around 10 cm 2 V -1 s -1 . By using high-resolution scanning transmission electron microscopy and atomic force microscopy, we find significant differences in the surface morphologies of the substrates after annealing and of the layers in dependence on their miscut direction. While substrates with miscuts toward  exhibit monolayer steps terminated by (201) facets, mainly bilayer steps are found for miscuts toward . Epitaxial growth on both substrates occurs in step-flow mode. However, while layers on substrates with a miscut toward  are free of structural defects, those on substrates with a miscut toward  are completely twinned with respect to the substrate and show stacking mismatch boundaries. This twinning is promoted at step edges by transformation of the (001)-B facets into (201) facets. Density functional theory calculations of stoichiometric low index surfaces show that the (201) facet has the lowest surface energy following the (100) surface. We conclude that facet transformation at the step edges is driven by surface energy minimization for the two kinds of crystallographically inequivalent miscut orientations in the monoclinic lattice of β-Ga 2 O 3 .