Ultrasmall sub-10 nm nanoprobes and carriers are of significant interest due to their favorable biodistribution characteristics in in vivo experiments. Here we describe the one-pot synthesis of PEGylated mesoporous silica nanoparticles with a single pore, tunable sizes around 9 nm and narrow size distributions that can be labeled with near-infrared dye Cy5.5. Particles are characterized by a combination of transmission electron microscopy, dynamic light scattering, fluorescence correlation spectroscopy, optical spectroscopy, nuclear magnetic resonance spectroscopy, and nitrogen sorption/desorption measurements. The possibility to distinguish an “inside” and “outside” may render these particles an interesting subject for further studies in sensing, drug delivery, and theranostics applications.