Octahedral Co3O4/carbon nanofiber (CNF) composites are fabricated using electrospinning and hydrothermal methods. Their morphological characteristics, chemical bonding states, and electrochemical properties are used to demonstrate the improved photovoltaic properties of the samples. Octahedral Co3O4 grown on CNFs is based on metallic Co nanoparticles acting as seeds in the CNFs, which seeds are directly related to the high performance of DSSCs. The octahedral Co3O4/CNFs composites exhibit high photocurrent density (12.73 mA/m2), superb fill factor (62.1 %), and excellent power conversion efficiency (5.61 %) compared to those characteristics of commercial Co3O4, conventional CNFs, and metallic Co-seed/CNFs. These results can be described as stemmnig from the synergistic effect of the porous and graphitized matrix formed by catalytic graphitization using the metal cobalt catalyst on CNFs, which leads to an increase in the catalytic activity for the reduction of triiodide ions. Therefore, octahedral Co3O4/CNFs composites can be used as a counter electrode for Pt-free dye-sensitized solar cells.