We investigated elucidating diffusional dynamics of the solvent located at the interfacial region between liquid media and the nanoporous structures of a silica sol-gel surface. by monitoring phosphorescence lifetime. This variation in time constant can probe the diffusional motion affecting the pore and reflects upon the entrapment conditions caused by the solvent. A comparative study among various solvents enables us to model a plausible inter-molecular interaction existent between silica-sol gel pores and a given solvent. The [Ru(bpy)3]2+ ion dopant encapsulated in a silica based sol-gel thin film was immersed in solvent, and the phosphorescence decay time from photo-excited MLCT (metal-ligand-charge-transfer) state was observed. The solvents used in this study were water, methanol, ethanol, 2-propanol, and glycerol. Solvent intrusion into the sol-gel entrapment environment over time was observed during a four weeks period at 25 oC. While most of the solvents caused minimal changes in the phosphorescence over time, the dopant when immersed in water exhibited a linear monotonic increase dependent on the number of days immersed. The decay time observed in water approaches that of an aqueous solution after 21st days. This indicates that all cavities were becoming occupied by sufficient water to cause a freely mobile dopant analogous to an aqueous solution. These results strongly suggest that the permeability rate at a silica gel - liquid interface is dominated by a hydrogen bonding formation between solvent and a lone pair of oxygen of silanol groups and not by an electrostatic interaction with solvent and the [Ru(bpy)3]2+ ion dopant.