Fluorescence lifetime (FL) analysis and fluorescence correlation spectroscopy (FCS) have been successfully employed to reveal detailed information about the internal architecture of fluorescent silica nanoparticles (NPs). The dual-component lifetime behavior shows a two-domain dye distribution in the NP as a function of solvent accessibility. The introduction of an undoped silica shell serves to stabilize the outer dye fraction that is manifest as an increase in lifetime. The FCS not only shows a size-dependent increase in the cross-correlation decay constant but also demonstrates a significant relaxation in the FCS signal with the introduction of an undoped silica shell.