Samaria-doped ceria solid solutions were prepared by homogeneous precipitation with hexamethylenetetramine using water and mixtures of alcohol/water as solvent. The mixed solvent influences several physical properties of the synthesized material when compared to those of samples prepared in water. The solid solution is formed, at least partially, during precipitation as demonstrated by Raman spectroscopy data. The dried precipitate is crystalline and single phase with fluorite-type structure, and consists of a mixture of anhydrous and hydrated cerium oxide with average sizes in the 5–8 nm range. Thermal decomposition of the as-synthesized material occurs at 400 °C. High densification was obtained at low temperatures (∼1200 °C). The electrical conductivity of grains and grain boundaries is improved for synthesized samples when compared to specimens prepared by mixing of starting oxides. These improved characteristics of synthesized powders are attributed to the interaction among the solvent and hydroxyl and water species on the surface of nanoparticles. The strength of this interaction is related to the carbon content in the alcohol chain.