The electronic structure of epitaxial, predominantly single-crystalline thin films of zirconium diboride (ZrB2), a lattice-matching, conductive ceramic to GaN, grown on Si(111) was studied using angle-resolved ultraviolet photoelectron spectroscopy. The existence of Zr-derived surface states dispersing along the Γ¯-M¯ direction indicates a metallic character provided by a two-dimensional Zr-layer at the surface. Together with the measured work function, the results demonstrate that the surface electronic properties of such thin ZrB2(0001) buffer layers are comparable to those of the single crystals promising excellent conduction between nitride layers and the substrate in vertical light-emitting diodes on economic substrates.