ABSTRACT Interfaces containing misfit dislocations deteriorate electronic properties of heteroepitaxial wide bandgap III-nitride semiconductors grown on foreign substrates, as a result of lattice and thermal expansion mismatches and incompatible chemical bonding. We report grain-boundary-free AlN nucleation layers (NLs) grown by metalorganic chemical vapor deposition on SiC (0001) substrates mediated by an interface extending over two atomic layers L1 and L2 with composition (Al1/3Si2/3)2/3N and (Al2/3Si1/3)N, respectively. It is remarkable that the interfaces have ordered vacancies on one-third of the Al/Si position in L1, as shown here by analytical scanning transmission electron microscopy and ab initio calculations. This unique interface is coined the out-of-plane compositional-gradient with in-plane vacancy-ordering and can perfectly transform the in-plane lattice atomic configuration from the SiC substrate to the AlN NL within 1 nm thick transition. This transmorphic epitaxial scheme enables a critical breakdown field of ∼2 MV/cm achieved in thin GaN-based transistor heterostructures grown on top. Lateral breakdown voltages of 900 V and 1800 V are demonstrated at contact distances of 5 and 20 μm, respectively, and the vertical breakdown voltage is ≥3 kV. These results suggest that the transmorphic epitaxially grown AlN layer on SiC may become the next paradigm for GaN power electronics