Ceria is widely used in industrial fields due to its unique chemical properties. In this work, a series of CeO2 particles with controllable morphology, size, and defect concentration were obtained by a simple molten salt method. The adjustment of temperature and molten salt concentration has a considerable effect on the morphology and particle size of the final CeO2 particles while prolonging the holding time has little effect. Ion doping and reducing atmosphere calcination were used to regulate the defect concentration to improve the chemical activity of CeO2 particles. SEM results show that the morphology of CeO2 particles transforms from sphere to octahedron under the two treatments. The Rietveld refinement results and the XPS spectra indicate that increasing calcination temperature, reducing atmosphere calcination and ion doping are beneficial to improving the oxygen vacancies and Ce3+ concentration of CeO2 samples, which are the reason for enhancing the photocatalytic activity of the samples. Moreover, the oriented attachment, agglomeration and merging of crystals formed by the decomposition of cerium precursors are the key to the growth of CeO2 particles. Aggregates with exposed low-energy planes merge directly to form particles of various morphologies to maintain their own low energy.