The electrical properties of individual p- and n-type silicon microwires have been investigated using a direct contact formation technique, in which an Ohmic contact between the tungsten probe and microwire was produced by applying mechanical force to the probe/microwire junction. This method alleviated the need for lithography or a high-temperature process to form a metal/Si ohmic contact. The technique was also used to characterize the Si microwire/conducting polymer junctions in a single cell of a membrane-supported bilayer Si microwire structure that is of interest for the direct production of fuels from sunlight. The data indicate that the combination of PEDOT–PSS–Nafion and highly doped Si microwires is suitable, from an electrical resistance perspective, to be used in a solar fuels generation device.