<jats:title>Abstract</jats:title><jats:p>Non‐toxic InP‐based nanocrystals have been developed for promising candidates for commercial optoelectronic applications and they still require further improvement on photophysical properties, compared to Cd‐based quantum dots (QDs), for better device efficiency and long‐term stability. It is, therefore, essential to understand the precise mechanism of carrier trapping even in the state‐of‐the‐art InP‐based QD with near‐unity luminescence. Here, it is shown that using time‐resolved spectroscopic measurements of systematically size‐controlled InP/ZnSe/ZnS core/shell/shell QDs with the quantum yield close to one, carrier trapping decreases with increasing the energy difference between band‐edge and trap states, indicating that the process follows the energy gap law, well known in molecular photochemistry for nonradiative internal conversion between two electronic states. Similar to the molecular view of the energy gap law, it is found that the energy gap between the band‐edge and trap states is closely associated with ZnSe phonons that assist carrier trapping into defects in highly luminescent InP/ZnSe/ZnS QDs. These findings represent a striking departure from the generally accepted view of carrier trapping mechanism in QDs in the Marcus normal region, providing a step forward understanding how excitons in nanocrystals interact with traps, and offering valuable guidance for making highly efficient and stable InP‐based QDs.</jats:p>