We report on femtosecond to millisecond pump–probe experiments performed on a multilayered structure composed by the alternation of CdSe nanocrystals (NCs) and poly(p-styrenesulphonic acid) (PSSH). We found that, after a few picoseconds of pumping at high intensity, an intense photoinduced absorption band and a strong derivative feature emerge in the differential absorption spectrum, both overlapping with the positive bleaching bands of the filled exciton states. These two former spectral features are long-living well into the millisecond range, and we attribute them to the population of charged trap states, located close to the NC surface, and thus inducing a Stark effect through the strong electric field they generate inside the NC.