Integral molar enthalpies of mixing were determined by drop calorimetry for (Ag-Li) liquid alloys at two temperatures (1253 and 873) K. The integral molar enthalpies of mixing are negative in the entire range of concentrations. For the mole fraction of lithium X-Li = 0.5664, minimum value of the integral enthalpy of mixing of at Delta H-m = -11.679 kJ/mol was observed. For (Ag-Li) liquid alloys, between T = (873 and 1253) K no temperature dependence was observed. Ab initio molecular dynamics was used to simulate liquid phase structures at T = 873 K (Li-rich side) and at T = 1250 K (Ag-rich phase) for subsequent calculation of the vibrational energy, respectively. Our measured and calculated data were compared with literature data. (C) 2014 Elsevier Ltd. All rights reserved.