In this study, (Bi2O3)(1-x-y)(Sm2O3)(x)(CeO2)(y) ternary system was synthesized by using solid-state reaction method. Structural, morphological, thermal and electrical properties of the samples were evaluated by means of X-ray diffraction (XRD), scanning electron microscopy, thermo gravimetry/differential thermal analyzer and four-probe method. The XRD measurement results indicated that the samples (x = 10-15, y = 5-10-15-20) had cubic -phase crystallographic structure. The phase stability of the samples was checked by the differential thermal analyzer measurements, which indicates most of the samples have stable -Bi2O3 phase. The electrical conductivity measurement results showed that the electrical conductivity increased with mol% CeO2 molar ratio at a fixed molar ratio of Sm2O3. The highest electrical conductivity obtained for the (Bi2O3)(0.65)(Sm2O3)(0.15)(CeO2)(0.20) system was 1.55 x 10(-2) (.cm)(-1) at 600 degrees C. The activation energies were also calculated at low temperature range (350-650 degrees C) which vary from 1.1325 to 1.4460eV and at high temperature (above 650 degrees C) which vary from 0.4813 to 1.1071 eV.