In this study, the ultrafast photo-induced carrier dynamics of red-emitting PQDs during structural degradation was investigated using time-resolved transient absorption spectroscopy. The spectroscopic analysis revealed how the carrier dynamics varied when PQDs were exposed to a polar solvent. Three decay modes (carrier trapping, radiative carrier recombination and trap-assisted non-radiative recombination) were proposed to analyze the carrier dynamics of PQDs. The light-emitting property of PQDs is primarily influenced by radiative carrier recombination. This study demonstrates that structural degradation induced halide migration within PQDs and the formation of defects within the crystal lattice, leading to a proliferation of carrier trapping states. The increased trap states led to a reduction in carriers undergoing radiative carrier recombination. Additionally, PQDs degradation accelerated radiative carrier recombination, indicating a faster escape of carriers from excited states. Consequently, these factors hinder carriers remaining in excited states, leading to a decline in the light-emitting property of PQDs. Nevertheless, increasing an excitation fluence could reduce the carrier trapping mode and increase the radiative carrier recombination mode, suggesting a diminishment of the impact of carrier trapping. These findings offer a more comprehensive understanding of structural degradation of PQDs and can contribute to the development of PQDs with high structural stability.