We study the interaction of liquid organic solvents within the pores of n- and p-type porous silicon (PSi) interfaces. Several polar (acetone, methanol, ethanol, isopropanol, and water), borderline (chloroform), and nonpolar (toluene and isoprene) molecular solvents have been characterized on distinct n- and p-type pore structures, as analyzed using scanning electron microscopy. Fundamental to these studies has been the generation of Nyquist diagrams comparing the behavior for both dry and solvent treated interfaces for each system studied. The results of these studies on an undecorated PSi interface suggest a closer correlation with the dipole moments associated with the applied organic solvents rather than their dielectric response. This is supported by the observed interaction of the considered solvents with metal oxide (AuxO (x ≫ 1) and SnOx) decorated PSi interfaces where nanostructured metal oxide-solvent dipole–dipole interactions appear to be manifest. In correlation with the Nyquist plots and the...