Photoelectrochemical cells (PEC) are appealing devices for the production of renewable energy carriers. In this context, III-V semiconductors such as GaAs are very promising materials due to their tunable band gaps, which can be appropriately adjusted for sunlight harvesting. Because of the high cost of these semiconductors, the nanostructuring of the photoactive layer can help to improve the device efficiency as well as drastically reduce the amount of material needed. III-V nanowire-based photoelectrodes benefit from the intrinsically high aspect ratio of nanowires, their enhanced ability to trap light, and their improved charge separation and collection abilities and thus are particularly attractive for PECs. However, III-V semiconductors often suffer from corrosion in aqueous electrolytes, preventing their utilization over long periods under relevant working conditions. Here, photocathodes of GaAs nanowires protected with thin TiO2 shells were prepared and studied under simulated sunlight irradiation to assess their photoelectrochemical performances in correlation with their structural degradation, highlighting the advantageous nanowire geometry compared to its thin-film counterpart. Morphological and electronic parameters, such as the aspect ratio of the nanowires and their doping pattern, were found to strongly influence the photocatalytic performances of the system. This work highlights the advantageous combination of nanowires featuring a buried radial p-n junction with Co nanoparticles used as a hydrogen evolution catalyst. The nanostructured photocathodes exhibit significant photocatalytic activities comparable with previous noble-metal-based systems. This study demonstrates the potential of a GaAs nanostructured semiconductor and its reliable use for photodriven hydrogen production.