Perovskite-type materials have been investigated extensively in the attempt to discover new electrolyte materials for solid oxide fuel cells (SOFC) operating at low temperatures. These materials include LaAlO3-based perovskite, which, when adequately doped, presents high ionic conductivity. However, despite the high conductivity of doped LaAlO3, two characteristics limit its application as solid electrolyte: low sinterability and p-type electronic conductivity in oxidizing conditions. The purpose of this work was to investigate the effect of Pr co-doping on the densification and electrical conductivity of Sr-doped LaAlO3. The addition of Pr eliminated the deficiencies mentioned above. Pr in solid solution acts as a perfect sintering aid because promoted densification without forming secondary phase which should be detrimental for electrical conduction. The addition of Pr also increased the bulk electrical conductivity measured in air atmosphere but had no effect at low oxygen partial pressure. However, the addition of Pr had a strong effect on the grain boundary, improving the ionic grain boundary electrical conductivity at air atmosphere which was attributed to the Pr influence on the space charge layer.