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Cesium lead bromide (CsPbBr 3 , CPB) powder formed by micro-, nanocrystals (MC, NC) and quantum dots (QD) was synthesized as free-standing and polystyrene covered. Luminescence was multicomponent, in general, ranging from below 1.9 eV up to about 2.6 eV. The ultrafast decay kinetics exhibited strong decay time component with the value of 260 ps. Electron paramagnetic resonance (EPR) revealed surface defects like O 2 − and some spin transitions most likely originating from some complex defect, supposedly F-V k (H) dimer center under the constant ultraviolet (UV) light irradiation at the temperature T = 10 K. The thermal release of the electrons from the O 2 − center was correlated with the 117 K thermally stimulated luminescence (TSL) peak. Coating with polystyrene resulted in the about doubly increased decay time of luminescence. The O 2 − and F-V k (H) EPR resonances were not observed as well. The TSL peak which might be ascribed to the O 2 − was not clearly detected anymore. The glow curve was composed of one very broad peak typical for the amorphous materials. At the same time, the polystyrene prevented the MCs creation. The existence of charge/energy transfer between the CPB and polystyrene due to the chemical bonding was assumed and confirmed also by calculations. [Display omitted] • EPR, TSL and RL study of charge trapping and luminescence in CsPbBr 3. • Charge/energy transfer was detected. • O 2 − -related electron trapping center was revealed in these crystals. • TSL peak was correlated to the release of electrons from the O 2 − surface center. • Complex bromine vacancy-related charge trapping center was observed. [ABSTRACT FROM AUTHOR]