Rapid synthesis of ultralong silver nanowires (AgNWs) has been obtained using a one-pot polyol-mediated synthetic procedure. The AgNWs have been prepared from the base materials in less than one hour with nanowire lengths reaching 195 μm, which represents the quickest synthesis and one of the highest reported aspect ratios to date. These results have been achieved through a joint analysis of all reaction parameters, which represents a clear progress beyond the state of the art. Dispersions of the AgNWs have been used to prepare thin, flexible, transparent and conducting films using spray coating. Due to the higher aspect ratio, an improved electrical percolation network is observed. This allows a low sheet resistance (RS = 20.2 Ω/sq), whilst maintaining high optical film transparency (T = 94.7%), driving to the highest reported figure-of-merit (FoM = 338). Owing to the light-scattering influence of the AgNWs, the density of the AgNW network can also be varied to enable controllability of the optical haze through the sample. Based on the identification of the optimal haze value, organic photovoltaics (OPVs) have been fabricated using the AgNWs as the transparent electrode and have been benchmarked against indium tin oxide (ITO) electrodes. Overall, the performance of OPVs made using AgNWs sees a small decrease in power conversion efficiency (PCE), primarily due to a fall in open-circuit voltage (50 mV). This work indicates that AgNWs can provide a low cost, rapid and roll-to-roll compatible alternative to ITO in OPVs, with only a small compromise in PCE needed.