An organic thiolate/disulfide redox couple with low absorption in the visible region was developed for use in fabricating novel dye-sensitized photovoltaic wires with an aligned carbon nanotube (CNT) fiber as the counter electrode. These flexible wire devices achieved a maximal energy conversion efficiency of 7.33%, much higher than the value of 5.97% for the conventional I(-)/I3(-) redox couple. In addition, the aligned CNT fiber also greatly outperforms the conventional Pt counter electrode with a maximal efficiency of 2.06% based on the thiolate/disulfide redox couple.