Metal/semiconductor superlattices represent a fascinating frontier in materials science and nanotechnology, where alternating layers of metals and semiconductors are precisely engineered at the atomic and nano‐scales. Traditionally, epitaxial metal/semiconductor superlattice growth requires constituent materials from the same family, exhibiting identical structural symmetry and low lattice mismatch. Here, beyond this conventional constraint, a novel class of epitaxial lattice‐matched metal/semiconductor superlattices is introduced that utilizes refractory hexagonal elemental transition metals and wide‐bandgap III‐nitride semiconductors. Exemplified by the Hf/AlN superlattices exhibiting coherent layer‐by‐layer epitaxial growth, cross‐plane thermionic emission is observed through current–voltage measurements accomplished for the first time in any metal/semiconductor superlattices. Further, thermoreflectance measurements reveal significant enhancement in cross‐plane Seebeck coefficients attributed to carrier energy filtering by Schottky barriers. Demonstration of artificially structured elemental‐metal/wide‐bandgap compound‐semiconductor superlattices promises to usher in new fundamental physics studies and cutting‐edge applications such as tunable hyperbolic metamaterials, quantum computing, and thermionic‐emission‐based thermoelectric and thermophotonic energy conversion devices.