Phase equilibria and thermodynamic properties of the Co-Hf system were investigated via calorimetric measurements, first-principles calculations and thermodynamic modeling. Heat contents of Co2Hf and CoHf2 were measured by drop calorimetry from 300 to 1200 degrees C. The enthalpy of formation for Co23Hf6 at OK was computed via first-principles calculations. Based on the experimental measurements and first-principles calculations from the present work and the literature, the Co-Hf system was assessed by means of CALPHAD (CALculation of PHAse Diagram) approach. The excess Gibbs energy of solution phases was modeled with Redlich-Kister polynomial. Sublattice models were employed to describe the homogeneity ranges of Co2Hf, CoHf and CoHf2. The order-disorder transition between B2 (CoHf) and A2 (MO phases was taken into account in the current optimization. Using the optimized parameters, glass forming range (GFR) of the Co-Hf amorphous alloys was predicted to be 15-75 at.% Hf, which is in satisfactory agreement with the experimental observation. (C) 2015 Elsevier B.V. All rights reserved.