Modern engineering fields put forward requirements for optical temperature sensors, which need natural-light excitation/storage and near-infrared (NIR) afterglow emission for some special conditions. Here, NIR persistent luminescent phosphors of ZnGa 2−x (Mg/Ge) x O 4 :Cr 3+ (x = 0−1.25) have been synthesized. The incorporation of Mg 2+ /Ge 4+ ions in ZnGa 2 O 4 :Cr 3+ resulted in more defect clusters of "Mg Ga ′ −Ge Ga• " and "Zn Ga ′ −Ge Ga • " and interstitial oxygens (O Int ). Increasing the calcination temperature and Mg 2+ /Ge 4+ doping both contributed to the generation of O Int . Higher efficiency of visible light excitation was observed, mainly due to the defect clusters and O Int. The samples exhibited a bright NIR emission at 695 nm by exposure to UV or visible light, and the NIR signal can last longer than 1 h after the stoppage of excitation. Incorporation of Mg 2+ /Ge 4+ and increasing the calcination temperature both resulted in a deeper trap depth. However, the density of trapped charge carriers takes the dominant role in the persistent luminescence. Therefore, the x = 0.25 sample, having the most trapped charge carriers, exhibits the best afterglow performance. The prepared phosphor exhibited a temperature-dependent persistent luminescence behavior, which can charge natural light and release NIR light repeatedly many times, indicating that they are the potential natural-light rechargeable materials for temperature sensing.