The Sc-Ni binary system was investigated via a hybrid of experiment and thermodynamic calculation. Eleven alloys were prepared by arc melting. The as-cast and annealed samples were analyzed by means of X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectrometer, electron probe microanalysis and differential thermal analysis/differential scanning calorimetry. The invariant reactions on Sc-rich side were reinvestigated. Five compounds (ScNi5, Sc2Ni7, ScNi2, ScNi and Sc2Ni) were observed in the present experiment. Their enthalpies of formation at 0 K were computed via first-principles calculations to supply referable thermodynamic data for the modeling. One single function was used to describe the Gibbs energies of both the ordered Bcc_B2 (ScNi) and disordered Bcc_A2 phases. The presently obtained thermodynamic parameters for the Sc-Ni system can reproduce the experimental data reasonably. (C) 2014 Elsevier B.V. All rights reserved.