In this paper, various microstructures of Ce2(WO4)3 and Ce10W22O81 were prepared by applying a hydrothermal synthesis, in a ligand-free environment, and in the presence of a dioctyl sodium sulfosuccinate (DSS) surfactant, after which the materials were heat treated at a temperature of 900 °C. Depending on the ratio of cerium ions to sodium tungstate, as well as the reaction pH, two different cerium tungstate materials were obtained. The source of cerium, and the presence or absence of the surfactant had a significant influence on the morphology of the final product. The photoluminescence properties of Tb(3+) doped cerium tungstate materials were investigated. Luminescence measurements showed an efficient charge transfer from the tungstate groups to the Tb(3+) ions. All the materials emitted blue or green light under UV excitation.