In an effort to develop low-cost solar energy conversion techniques, high uniformity vertically oriented silicon wire arrays have been fabricated. These arrays, which allow for radial diffusion of minority charge carriers, have been measured in a photoelectrochemical cell. Large photovoltages (similar to 400 mV) have been measured, and these values are significantly greater than those obtained from the substrate alone. Additionally, the wire array samples displayed much higher current densities than the underlying substrate, demonstrating that significant energy conversion was occurring due to the absorption and charge-carrier transport in the vertically aligned Si wires. This method therefore represents a step toward the use of collection-limited semiconductor materials in a wire array format in macroscopic solar cell devices.