In this study, the surface convergence, surface energy, and work function on various crystal facets of ZrB2 were investigated by using the density functional theory calculations. Zr-terminated surface exhibits is more stable than the B-terminated surface. The electronic structure calculation reveals that ZrB2 exhibits metallic property, and the high density of states near the Fermi level is mainly composed of Zr-d and B-p orbitals. The work function values of the Zr-terminated (0001), (101¯0), (112¯0), and (112¯1) surfaces of ZrB2 are 4.52, 3.83, 4.00, and 2.56 eV, respectively. We found that the surface energy and work function of ZrB2 (112¯1) are the lowest compared to ZrB2 (0001), (101¯0) and (112¯0) surfaces, exhibiting good surface energy stability and providing excellent electron emission performance. This work provides valuable theoretical guidance for the exploration of ZrB2 as a novel cathode material for electron emission.