Perovskite quantum dots (QDs) are of great interest due to their outstanding optoelectronic properties and tremendous application potential. Improving photoluminescence (PL) spectra in all-inorganic perovskite QDs is of great importance for performance enhancement. In this work, the PL quantum yield of the CsPbBr3 perovskite QDs is enhanced from 70% to 95% with increasing radiation pressure. Such enhancement is attributed to the increased binding energy of self-trapped excitons (STEs) upon radiation pressure, which is consistent with its blue-shifted PL and other characterization results. Furthermore, we study ultrafast absorption spectroscopy and find that the dynamics of relaxation from free excitons to STEs in radiation pressure CsPbBr3 QDs is ascribed to stronger electron–phonon coupling in the contracted octahedral structure. It is further demonstrated that radiation pressure can boost the PL efficiency and explore effectively the relationship between the structure and optical properties.