CsPbBr3 perovskite quantum dots (QDs) show great potential in various applications due to their size-dependent and excellent optoelectronic properties. However, it is still challenging to synthesize size-tunable CsPbBr3 QDs with purple emission. Herein, CsPbBr3 nanospheres (NS) with purple emission (432 nm) and wavelength-tunable photoluminescence were synthesized using a two-step recrystallization method for the first time. A nanocube (NC) strategy resulting from CsPbBr3 nanosphere self-assembly via polar solvent-induced surface ligand mismatch was proposed. The self-assembly process endows the QDs with wavelength-tunable photoluminescence ranging from 432 to 518 nm. The significant reduction in defects during self-assembly was confirmed by transient optical spectroscopy measurements, photoluminescence quantum yields (PLQY), and the disappearance of tail bands in the long-wavelength region of the photoluminescence (PL) spectrum. This theory demonstrated that the decrease in high defect surfaces and increase in specific surface area were the reasons for the decline in defects. Most importantly, these QDs could be used for the active jamming of optical imaging systems based on charged-coupled devices (CCDs), including laser imaging radar and low light level (LLL) night vision systems. QDs significantly increase the mean square error (MSE) of the image, while the detection rate of the target by the artificial intelligence algorithm decreased by 95.17%. The wide wavelength tunable emission caused by structural changes makes it arduous for silicon-based detectors to avoid the interference of QDs by adding filters or by other means.