Adsorption and transport in hierarchical materials are investigated by means of adsorption and nuclear magnetic resonance experiments. Using micro/mesoporous zeolites with well-defined mesoporosity, we show that adsorption at a given pressure can be described as a simple linear combination of the adsorbed amounts taken at the same pressure for the pure microporous (zeolite FAU-Y) and mesoporous (Al-MCM-41) solids. Such a quantitative decomposition allows us to demonstrate the ability of diffusion measurements by Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR) to probe interconnectivity in hierarchical solids. On the one hand, transport in the mechanical mixtures can be described as the superimposition of diffusion in pure microporous and mesoporous solids. On the other hand, PFG NMR for the hierarchical sample provides an effective diffusivity that is intermediate between those for the pure zeolite and mesoporous silica. Furthermore, this effective diffusivity is slower than the linear combination of the two diffusivities weighted by the number of molecules present in each phase (used in the independent domain and fast-exchange theories) clearly showing interconnectivities and transfer limitations between the microporous and mesoporous domains. We also discuss the ability of combining theories such as the fast exchange model and the effective medium theory to quantitatively predict diffusion in such microporous/mesoporous materials.