Addition of butylamine to a solution of colloidal CdSe nanoparticles (NPs) caused a decrease in fluorescence intensity, with no effect on the picosecond bleach recovery of the exciton formation or on the luminescence dynamics. The relative fluorescence quantum yield was found to decrease with increasing butylamine concentration and to level off at high concentrations, but the fluorescence lifetimes were not influenced. The nonlinear concentration dependence of the fluorescence quantum yield did not follow the Stern-Volmer equation. This is in agreement with the observation that the CdSe luminescence lifetime was not affected by the addition of butylamine. A mechanism is proposed in which the emission observed in CdSe is assumed to result from the combination of surface-trapped electrons and holes. n-Butylamine occupies hole sites, thus blocking the recombination process, which results in decreasing the density of luminescent centers. These results will be discussed in terms of the nature of the binding sites of the amine on the nanoparticle surface.