Co-embedded graphitic porous carbon nanofibers(Co-GPCNFs) are synthesized by using an electrospinning method. Their morphological, structural, electrochemical, and photovoltaic properties are investigated. To obtain the optimum condition of Co-GPCNFs for dye-sensitized solar cells(DSSCs), the amount of cobalt precursor in an electrospinning solutuion are controlled to be 0 wt%(conventional CNFs), 1 wt%(sample A), and 3 wt%(sample B). Among them, sample B exhibited a high degree of graphitization and porous structure compared to conventional CNFs and sample A, which result in the performance improvement of DSSCs. Therefore, sample B showed a high current density(JSC, 12.88 mA/cm2) and excellent power conversion efficiency(PCE, 5.33 %) than those of conventional CNFs(12.00 mA/cm2, 3.78 %). This result can be explained by combined effects of the increased contact area between the electrode and elecytolyte caused by improved porosity and the increased conductivity caused by the formation of a high degree of graphitization. Thus, the Co-GPCNFs may be used as a promising alternative of Pt-free counter electrode in DSSCs.