The emergence of transition metal dichalcogenides (TMD) as an exciting class of materials with appealing potentials in electronic and optoelectronics has drawn intensive attention in the past few years. Herein, we report the fabrication of NiSe2, which has been predicted to be a promising candidate in the field of electrocatalyst, by direct selenylation of the nickel substrate after epitaxial growth of selenium on a nickel foil. With a combination of photoelectron spectroscopy (PES), X-ray diffraction (XRD), scanning electron microscopy (SEM) and density function theory (DFT) calculations, it is possible to identify the phase transition among the previously reported stable Ni-Se phases and the ultimate formation of NiSe2 species by external annealing at varying temperatures. While SEM reveals the morphology of NiSe2 film with flat terraces, XRD, XPS and DFT calculations demonstrate that NiSe2 is the relatively stable phase formed on the Ni substrate from the cohesive energy point of view. Furthermore, valence band spectra point out the nonmetallic level of these different Ni-Se compounds, agreeing well with literature reports. In the end, our report may indicate a feasible approach to synthesize the pure NiSe2 species under solution-free condition and an encouraging step forward towards non-noble electrocatalysts. (C) 2017 Elsevier B.V. All rights reserved.