Hollow micro/nanostructured CeO2‐based materials (HMNCMs) have triggered intensive attention as a result of their unique structural traits, which arise from their hollowness and the fascinating physicochemical properties of CeO2. This attention has led to widespread applications with improved performance. Herein, a comprehensive overview of methodologies applied for the synthesis of various hollow structures, such as hollow spheres, nanotubes, nanoboxes, and multishelled hollow spheres, is provided. The synthetic strategies toward CeO2 hollow structures are classified into three major categories: 1) well‐established template‐assisted (hard‐, soft‐, and in situ template) methods; 2) newly emerging self‐template approaches, including selective etching, Ostwald ripening, the Kirkendall effect, galvanic replacement, etc.; 3) bottom‐up self‐organized formation synthesis (namely, oriented attachment and self‐deformation). Their underlying mechanisms are concisely described and discussed in detail, the differences and similarities of which are compared transversely and longitudinally. Niche applications of HMNCMs in a wide range of fields including catalysis, energy conversion and storage, sensors, absorbents, photoluminescence, and biomedicines are reviewed. Finally, an outlook of future opportunities and challenges in the synthesis and application of CeO2‐based hollow structures is also presented.

Surface defects including oxygen vacancies and Ce3+ ions on the surface of CeO2 nanorods lead to an efficient catalytic activity towards water oxidation under visible light.

Complex oxide YVO multi-shell hollow spheres with uniform morphologies and controllable shell numbers are successfully prepared by using a newly developed and general composite yttrium-carbonaceous sphere templated approach. The prominent upconversion luminous intensity of the YVO :Yb /Er hollow spheres might be attributed to the enhanced near-infrared excitation light harvesting efficiency originated from the multiple reflections.

Multishell Y2 O3 :Yb(3+) /Er(3+) hollow spheres with uniform morphologies and controllable inner structures are prepared successfully by using a glucose-template hydrothermal process followed by temperature-programmed calcination. Much enhanced upconverted photoluminescence of these Y2 O3 :Yb(3+) /Er(3+) are observed, which are due to the multiple reflections and the enhanced light-harvesting efficiency of the NIR light resulting from the special features of the multishell structures.

A CuCo(O)-embedded nitrogen-enriched porous carbon framework catalyst derived from doped metal–organic frameworks for efficient hydrolysis of ammonia borane.