The insertion of fluorescently labeled thiols into the protecting self-assembled monolayer on the surface of gold nanoparticles through place exchange reactions and the effects of this insertion on the photophysical properties of the fluorophores are investigated. Analysis of solution-phase fluorescence data using a dynamic equilibrium model yields the equilibrium constant for the place exchange equilibrium, as well as the relative fluorescence brightness of the fluorophores on the particle surface. In all cases we find a significant quenching of the fluorescence, and potential reasons for this quenching are discussed. In the case of these relatively small particles (4.5 nm diameter), the quenching appears to be mainly related to enhanced nonradiative deactivation pathways. The place exchange equilibrium constant reveals a reduced affinity of the fluorescently labeled thiols for insertion into the nonfluorescent alkylthiol monolayer (K-eq approximate to 0.2) compared to unlabeled alkylthiols.