High-pressure water vapor annealing (HWA) was recently demonstrated as a method that can substantially improve the photoluminescence quantum yield (PLQY) of silicon quantum dots (Si QDs) with the oxide shell. In this Letter, the mechanism of this enhancement is studied optically on a single-dot level. HWA treatment is performed on Si QDs formed on a silicon-on-insulator wafer, and their photoluminescence (PL) properties were examined before and after the treatment. Our experiments show a 2.5 time enhancement in the average blinking duty cycle of Si QDs after 2.6 MPa HWA treatment without changing the average ON-state PL intensity. This observation proves the carrier trapping process is suppressed on the HWA-built Si/SiO2 interface. We also discussed the mechanism behind the PLQY enhancement of HWA-treated Si QDs by comparing single-dot-level data to reported ensemble PL Si QDs results. HWA treatment is found to mainly brighten “grey” (not 100% efficient) QDs, a mechanism different from changing dark (non-emitting) to bright (100% efficient) Si QDs by ligand passivation.