Understanding liquid-solid interactions in porous structures is crucial to evaluate connectivity and wettability, which are essential for applications in fuel cells, batteries, oil recovery, and more generally in energy production and storage systems. While a large amount of research has been focused on correlating wettability and flow, there are still significant gaps in our understanding of fluid flow and pore connectivity in porous media.In this research, the nature of water adsorbed within pores of several porous media is probed with dielectric spectroscopy. The results are analyzed in terms of surface wettability and the specific chemistry of water. More specifically, the dielectric behavior is described in terms of water molecules forming a network of weakly connected islands composed of hydrogen bonded water molecules (clusters) within the pores where charge transport is accomplished by hopping of H+ ions between different sites. The results from the dielectric spectroscopy are correlated with a quantitative evaluation of the surface hydrophilicity using the Hansen Affinity Parameters calculated by measuring the stability of suspensions in various solvents using analytical centrifugation. These studies are a promising platform to understand the interfacial interaction of liquids in porous media with implications for chemical spill pollution remediation, the development of controlled-release materials in drug delivery systems, and battery technologies.