InP/ZnS core/shell quantum dots have shown extraordinary application potential in photocatalysis. In this work, we demonstrated by ultrafast spectroscopy that the electron transfer ability of InP/ZnSe/ZnS core/shell/shell quantum dots was better than that of InP/ZnS quantum dots, because the introduction of ZnSe midshell resulted in improved passivation and greater exciton delocalization. The temperature-dependent PL spectra indicate that the exciton-phonon coupling strength and exciton binding energy of InP/ZnSe/ZnS quantum dots are smaller than those of InP/ZnS quantum dots. Further photocatalytic hydrogen evolution testing revealed that the photocatalytic activity of InP/ZnSe/ZnS quantum dots was significantly higher than that of InP/ZnS quantum dots, and InP/ZnSe/ZnS quantum dots even demonstrated improved stability. This research deepened our understanding of carrier dynamics and charge separation of InP/ZnSe/ZnS quantum dots, especially highlighting the application potential of InP/ZnSe/ZnS quantum dots in photocatalytic hydrogen evolution.