Abstract: Rapid formation of radial p–n junctions on electroless-etched silicon nanowires (SiNWs) was successfully demonstrated. With a low-cost objective, a homemade nonhazardous diffusion source of high phosphor concentration annealed at a small thermal budget was used. The SiNW solar cell, with Au electrodes, has shown a power conversion efficiency of 8.41%, which is higher by 30% compared with its planar counterpart. The SiNW solar cell incorporates an inherent antireflection property, reduced diffusion length requirement, and broad-band spectral quantum efficiency. The evidence of a successful radial p–n junction formation in the NWs has been revealed through the help of a conducting atomic force microscope (AFM) scanning for the photogenerated currents on the fractured surfaces of the NWs. The demonstrated radial junction fabrication technique is believed to reduce the cost of production and promote widespread use of them.