A dye-sensitized solar cell is one of cost-competitive photovoltaic devices. For higher performance, all components have been actively studied and improved. However, Pt is still a dominant catalyst since first development although some catalytic materials were studied so far. Catalytic materials of counter electrode play an important role in the performance because it supplies electrons from counter electrode to electrolyte. Therefore, the catalytic activation of counter electrode is closely connected with the performance enhancement. In this work, Pt nano-fiber was fabricated by electrospinning and applied for the counter electrode. Its wide surface area is advantageous for good conductivity and catalytic activation. Morphological characteristics of nano-fibers were analyzed according to electrospinning conditions. Photovoltaic properties, cyclic voltammetry, impedance analysis verified the catalytic activation. Consequently, dye-sensitized solar cell with Pt nano-fiber electrospun at 5.0 kV of applied voltage had higher performance than conventional dye-sensitized solar cell with Pt thin film. This work is significant for related researches because all nano-fibers counter electrode material proposed so far never exceeded the performance of conventional Pt counter electrode.