Thermodynamic stability, taking account of the electronic and ionic structures in Liquid Ag-polyvalent metal alloys, has been discussed in comparison to other monovalent-polyvalent metal alloys. Liquid Ag-Zn, Ag-Ga, Ag-In and Ag-Sn alloys show some ordered states as seen in their S-CC(O), and have different electronic and ionic structures in Ag-and polyvalent metal-rich regions, respectively. S-CC(O) of Liquid Ag-Pb and Ag-Tl alloys has shown the tendency to phase separation.