In this work, a counter electrode (CE) made from a composite of electrospun carbon nanofibers (CNs) and MoO2 nanoparticles has been discussed for the first time as an efficient and low-cost Pt-free counter electrode (CE) for dye-sensitized solar cells (DSSCs). MoO2/carbon nanofiber composites (MoO2/CNs) were successfully prepared via a facile one-step hydrothermal method. The obtained MoO2/carbon electrode showed good chemical stability, lower charge transfer resistance and higher electrocatalytic activity as compared to the conventional Pt electrodes. The characteristics of DSSCs based on MoO2/CNs electrodes were analyzed using photocurrent density-voltage, cyclic voltammetry, Tafel polarization curve and electrochemical impedance spectroscopy measurements. The experimental results revealed that the MoO2/CNs electrodes exhibited the optimal electrode characteristics. The DSSCs based on MoO2/CNs electrodes displayed better photovoltaic conversion efficiency (7.6%) than the Pt counter electrodes (7.34%).