Microporous silicon membranes, fabricated by lithographic patterning and wet and dry silicon etching processes, were used to create arrays of micro-scale interfaces between two immiscible electrolyte solutions (muITIES) for ion-transfer voltammetry. These membranes served the dual functions of interface stabilization and enhancement of the rate of mass-transport to the interface. The pore radii were 6.5 microm, 12.8 microm and 26.6 microm; the pore-pore separations were ca. 20- to 40-times the pore radii and the membrane thickness was 100 microm. Deep reactive ion etching (DRIE) was used for pore drilling through the silicon, which had been previously selectively thinned by potassium hydroxide etching. DRIE produces hydrophobic fluorocarbon-coated internal pore walls. The small pore sizes and large pore-pore separations used resulted in steady-state voltammograms for the transfer of tetramethylammonium cation (TMA(+)) from the aqueous to the organic phase, whereas the reverse voltammetric sweeps were peak-shaped. These asymmetric voltammograms are consistent with the location of the ITIES at the aqueous side of the silicon membrane such that the organic phase fills the micropores. Comparison of the experimental currents to calculated currents for an inlaid disc micro-interface revealed that the interfaces were slightly recessed, up to 10 microm (or 10% of the pore length) in one case. Facilitated ion transfer, with an organic-phase ionophore, confirmed the location of the organic phase within the pores. These microporous silicon membranes offer opportunities for various analytical operations, including enhancing the rate of mass transport to ITIES-based sensing devices and stabilization of the ITIES for hydrodynamic applications.