Electrides are unique materials, whose anionic electrons are confined to interstitial voids, and they have broad potential applications in various areas. In contrast to the majority of inorganic electrides, in which the anionic electrons primarily consist of s-electrons of metals, electrides with anionic d-electrons are very rare. Based on first-principles electronic structure calculations, we predict that the layered transition metal chalcogenide Hf₂Se is a novel electride candidate with anionic d-electrons. Our results indicate that the anionic electrons confined in the Hf₆ octahedra vacancy between [Hf₂Se] layers mainly come from the Hf-5d orbitals. In addition, the anionic electrons coexist with the Hf–Hf multiple-center metallic bonds located in the center of neighboring Hf₄ tetrahedra. The calculated work function (3.33 eV) for the (110) surface of Hf₂Se is slightly smaller than that of Hf₂S, which has recently been reported to exhibit good electrocatalytic performance. Our study of Hf₂Se will enrich the electride family, and promote further research into the physical properties and applications of electrides.