AbstractA study of the dynamics of the electronic states of CdS semiconductor clusters grown in situ in reversed micelles via picosecond pump‐probe technique reveals efficient transient bleaching of the excitonic absorption. This effect is attributable mainly to hole localization near the trapped electron, with no evidence of electron ejection (forming a solvated electron) detectable despite the apparent proximity of the cluster to the included water pool. Bleaching efficiency is cluster‐size dependent, and recovery kinetics are governed by the nature of the particle surface. Similar decay behavior is observed in cluster fluorescence. Generally, the decay is characterized by two components, the faster attributed to recombination of a mobile, detrapped electron with a trapped hole, and the slower to an exchange interaction between trapped carriers. The observed strong multiexponentionality of the decay results from a distribution in trap energy levels, as well as from a distribution of distances between traps on the cluster surface. By varying preparation conditions, particles of different sizes with different surface defects can be grown in reversed micelles in a reproducible way so that their electronic properties can be control