The diffusion behavior of small molecules in hollow core shell nanocapsules was studied using pulsed field gradient NMR By purposefully selecting the liquid saturating the hollow core and the porous shell and the solvent between the nanocapsules, two different situations corresponding to the excluded and admitted molecular exchange between the intra- and intercapsule liquids at the external boundary of the nanoparticles were covered. In the former case, corresponding to the reflective boundary condition for the molecules approaching the nanocapsule boundary, restricted diffusion in the complex pore space formed by the hollow core and the mesoporous shell was observed. The time-dependent diffusivities measured in the experiment were inter-related with the geometry of the intraparticle pore space. The thus assessed structural information was found to be in a good agreement with that provided by electron microscopy. In the case of the molecular exchange occurring between the two pools of molecules in the nanocapsules and between them, the diffusive dynamics of only the molecules remaining in the nanocapsules during the entire observation times was studied.