Copper-based perovskites, with lower electronic dimensions and high photoluminescence quantum yields (PLQY), which are non-toxic and thermally stable, have been reported since 2019 and have immediately attracted great attention. So far, only a few studies have researched the temperature-dependent photoluminescence properties, posing a challenge in ensuring the stability of the material. In this paper, the temperature-dependent photoluminescence properties have been investigated in detail, and a negative thermal quenching of all-inorganic CsCu₂I₃ perovskites has been studied. Moreover, the negative thermal quenching property can be tuned with the assistance of citric acid, which has not been reported before. The Huang–Rhys factors are calculated to be 46.32/38.31, which is higher than for many semiconductors and perovskites.