Nano and micro (Bi2O3)1-x-y(Eu2O3)x(Er2O3)y (x = 0.1, 0.15, y = 0.05, 0.2) double-doped system materials are synthesized by exploiting solid-state synthesis techniques. When we use nano sized powders to synthesize the samples we call them nano; when we use micro sized powders, we call them micro. The thermal, structural, morphological and electrical properties of nano and micro structured electrolyte samples for solid oxide fuel cells (SOFCs) are characterized. As a result of XRD measurements, the face centered δ-Bi2O3 (cubic) phase is obtained for all nano samples. However, the mixed phase is obtained for some micro samples. The electrical measurements show that conductivity decreases when the amount of Er2O3 is increased. The principal conclusion of the study is that the size effect provides relatively good structural stability in intermediate temperature SOFCs (IT-SOFCs); also, the nano-Bi2O3 system has the lowest activation energy and demonstrates high electrical conductivity.