Photovoltaics (PVs) based on nanostructured III/V semiconductors can potentially reduce the material usage and increase the light-to-electricity conversion efficiency, which are anticipated to make a significant impact on the next-generation solar cells. In particular, GaAs nanowire (NW) is one of the most promising III/V nanomaterials for PVs due to its ideal bandgap and excellent light absorption efficiency. In order to achieve large-scale practical PV applications, further controllability in the NW growth and device fabrication is still needed for the efficiency improvement. This article reviews the recent development in GaAs NW-based PVs with an emphasis on cost-effectively synthesis of GaAs NWs, device design and corresponding performance measurement. We first discuss the available manipulated growth methods of GaAs NWs, such as the catalytic vapor-liquid-solid (VLS) and vapor-solid-solid (VSS) epitaxial growth, followed by the catalyst-controlled engineering process, and typical crystal structure and orientation of resulted NWs. The structure-property relationships are also discussed for achieving the optimal PV performance. At the same time, important device issues are as well summarized, including the light absorption, tunnel junctions and contact configuration. Towards the end, we survey the reported performance data and make some remarks on the challenges for current nanostructured PVs. These results not only lay the ground to considerably achieve the higher efficiencies in GaAs NW-based PVs but also open up great opportunities for the future low-cost smart solar energy harvesting devices.