Polypyrrole nanowires are facile synthesized under a mild condition with FeCl3 as an oxidant. Polypyrrole nanowires with the width of 120 nm form many nanogaps or pores due to the intertwined nanostructures. More importantly, PPy nanowires were further applied for supercapacitor electrode materials. After electrochemical testing, it was observed that the PPy nanowire based electrode showed a large specific capacitance (420 F g−1, 1.5 A g−1) and good rate capability (272 F g−1, 18.0 A g−1), which is larger than that of most of published results. The as-prepared electrode can work well even after 8000 cycles at 1.5 A g−1.