Nanostructured cerium oxide (CeO2) with outstanding physical and chemical properties has attracted extensive interests over the past few decades in environment and energy-related applications. With controllable synthesis of nanostructured CeO2, much more features were technologically brought out from defect chemistry to structure-derived effects. This review highlights recent progress on the synthesis and characterization of nanostructured ceria-based materials as well as the traditional and new applications. Specifically, several typical applications based on the desired ceria nanostructures are focused to showcase the importance of nanostructure-derived effects. Moreover, some challenges and perspectives on the nanostructured ceria are presented, such as defects controlling and retainment, scale-up fabrication, and monolithic devices. Hopefully, this review can provide an improved understanding of nanostructured CeO2 and offer new opportunities to promote the further research and applications in the future.