Periodic arrays of n-GaAs nanowires have been grown by selective-area metal–organic chemical-vapor deposition on Si and GaAs substrates. The optical absorption characteristics of the nanowire-arrays were investigated experimentally and theoretically, and the photoelectrochemical energy-conversion properties of GaAs nanowire arrays were evaluated in contact with one-electron, reversible, redox species in non-aqueous solvents. The radial semiconductor/liquid junction in the nanowires produced near-unity external carrier-collection efficiencies for nanowire-array photoanodes in contact with non-aqueous electrolytes. These anodes exhibited overall inherent photoelectrode energy-conversion efficiencies of ∼8.1% under 100 mW cm⁻² simulated Air Mass 1.5 illumination, with open-circuit photovoltages of 590 ± 15 mV and short-circuit current densities of 24.6 ± 2.0 mA cm⁻². The high optical absorption, and minimal reflection, at both normal and off-normal incidence of the GaAs nanowire arrays that occupy <5% of the fractional area of the electrode can be attributed to efficient incoupling into radial nanowire guided and leaky waveguide modes.