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Owing to the unique mechanism of photoelectron storage and release, long persistent phosphorescence, also called long persistent luminescence or long lasting afterglow/phosphorescence, plays a pivotal role in the areas of spectroscopy, photochemistry, photonics and materials science. In recent years, more research has focused on the manipulation of the morphology, operational wavebands and persistent duration of long persistent phosphors (LPPs). These desired achievements stimulated the growing interest in designing bio-labels, photocatalysts, optical sensors, detectors and photonic devices. In this review, we present multidisciplinary research on synthetic methods, afterglow mechanisms, characterization techniques, materials system, and applications of LPPs. First, we introduce the recent developments in LPPs for the synthesis of nanoparticles from the aspects of particle sizes, monodispersity and homogeneity based on the urgent application of bio-imaging. In the later sections, we present the possible mechanisms, which involve the variation of trap distribution during the trapping and de-trapping process, complicated photo-ionization reaction of trap site levels and impurity centers together with their corresponding migration kinetics of carriers. Meanwhile, we emphasize the characterization techniques of defects, used to qualitatively or quantitatively describe the types, concentrations and depths of the traps. This review article also highlights the recent advances in suggested LPPs materials with a focus on the LPPs' hosts and optically active centers as well as their control, tuning and intrinsic links. We further discuss the classification of LPPs based on the different emission and excitation wavebands from the ultraviolet to the near-infrared region along with an overview of the activation mode of afterglow. Afterwards, we provide an exhibition of new products towards diverse application fields, including solar energy utilization, bio-imaging, diagnosis, and photocatalysts. Finally, we summarize the current achievements, discuss the problems and provide suggestions for potential future directions in the aforementioned parts.