High purity, fine crystalline, degradation-free at low temperature powders have attracted special interest in CAD/CAM prosthetic dentistry full ceramic restorations. This study reports the preparation and characterisation of zirconia-ceria (0.9ZrO20.1CeO2) powders. Materials were obtained from zirconium-n-alkoxide and cerium nitrate hexahydrate in the pH 2–4 and 8–10. Methods: Zirconia-ceria powders were obtained with the sol-gel method in a humid-free environment. Thermal analysis (TGA/DTA) of the as-prepared materials was made for an assessment of its behaviour at elevated temperatures. Specimens were dried at 80°C and calcinated in two stages: at 300°C with soaking time 2.5 h and 850°C with holding time 2.5 h, in order to evaluate the phase transformations. Thermal analyses of the as-dried powders were made for an assessment of its thermal behaviour during heat treatment up to 1000 °C. By X-ray diffraction (XRD), polymorphs of ZrO2 were identified. Additionally, scanning electron microscopy (SEM) and laser particle size distribution (PSD) were involved for characterisation of morphology of the powders. Results: We found a correlation between the pH of the colloidal system and the morphology of the as-obtained powders. Based on analysis (SEM,PSD), structures were identified known as soft and hard agglomerates. Conclusions: In summary, it can be stated differences were found between powder morphology depending on the used pH, which can be crucial for powder densification during sintering and compacting green bodies which, as a consequence, may be crucial for the lifetime of zirconia prostheses. Correlations between phase composition and pH are difficult to grasp, and require further more sophisticated studies.