Persistent luminescence as a self-sustained optical phenomenon has promising applications in various fields, including safety signage, night-vision surveillance and information storage. Particularly, nano-scale near-infrared emitting afterglow probes with the advanced bioimaging technique have attracted increasing attention among the academic and industry community. The central objective of this research is to provide a convincing and innovative application and a deep-level explanation of near-infrared emitting persistent luminescent materials. This research will focus on the effective and environment-friendly synthesis of transition metal and/or lanthanide doped phosphors, the rational design and optimization of the persistent luminescence behavior. Moreover, some key challenges will be addressed, such as the utilization of efficient energy transfer within the second and third biological windows, the detailed information on the nature of traps, the wavelength/temperature dependent persistent luminescence behavior and the understanding of structure-property relation. A new combination of using energy transfer among dopants within near-infrared region and employing suitable electron release process is designed. The outcome of the project could open the avenue to motivate researchers to explore novel long afterglow phosphors in a design way instead of by trial and error approach.