Many activity measurements of components in liquid oxides have been reported in the field of slag chemistry. However, very little is known about the thermodynamic behavior of compo- nents in oxide solid solutions. In the present paper, e.m.fs. of the follow- ing galvanic cells employing solid electrolyte Zr02(CaO) were measured on the entire range of composition of the solid solutions. Pt/Ni-(Mgl-x ix)O/ZrO2(CaO)/Ni-NiO/Pt Pt/Ni-(Mgl-xNix)2SiO./ZrO2(CaO)/Ni-NiO/Pt Pt/Ni-(Mg l-xNix)Si03/ZrO2(CaO)/Ni-NiO/Pt. Activities of NiO in these solid solutions of (Mgl_ Nix)O and (Mgl_ Nix) 2Si0a(where 0< x <1) calculated from the results of e.m.f. measure- ments show considerable negative deviation from raoult's law, whereas (mgl_xnix)si03 (where 0>< x < 0.12) is slightly positive in the temperature interval studied in the present investigation, 800-1000C.