A phosphor with remarkable long persistent luminescence features, Zn₃Ga₂Sn₁O₈:0.5 Cr³⁺, suitable for deep and reproducible tissue imaging has been rationally designed and successfully fabricated. This phosphor shows bright and long persistent luminescence over 300 h in the near-infrared region, and permits an enabling long-term, reproducible, real-time and reliable structural imaging of deep tissues. Moreover, the revived luminescence and persistent luminescence under the excitation of near-infrared incoherent light are also demonstrated to reveal an optional multiplexed detection. This new luminescent indicator will allow repeatable visualization of the structural and functional processes in cells, tissues and other complex systems. In addition, multifarious and systematic investigations are successfully carried out to unravel the nature of traps and also to verify the rationality of the material design.

Scintillators, which can convert high‐energy ionizing radiation into visible light, have been serving as the core component in radiation detectors for more than a century of history. To address the increasing application demands along with the concern on nuclear security, various strategies have been proposed to develop a next‐generation scintillator with a high performance in past decades, among which the novel approach via structure control has received great interest recently due to its high feasibility and efficiency. Herein, the concept of “structure engineering” is proposed for the exploration of this type of scintillators. Via internal or external structure design with size ranging from micro size to macro size, this promising strategy cannot only improve scintillator performance, typically radiation stopping power and light yield, but also extend its functionality for specific applications such as radiation imaging and therapy, opening up a new range of material candidates. The research and development of various types of structured scintillators are reviewed. The current state‐of‐the‐art progresses on structure design, fabrication techniques, and the corresponding applications are discussed. Furthermore, an outlook focusing on the current challenges and future development is proposed.