A new type of counter electrode material Bismuth molybdate/carbon nanofibers (Bi2MoO6/CNFs) composite is synthesized by electrospinning and simple hydrothermal method and further used in dye-sensitized solar cells (DSSCs) on Titanium (Ti) mesh substrate, which shows strong stability and sustainable utilization. The introduction of titanium mesh and high catalytic activity of Bi2MoO6/CNFs materials provide a low transmission resistance and a large number of active sites that benefit electron transfer and the reduction I3− to I−. A series of electrochemical measurements reveal that the DSSCs device assembled with Bi2MoO6/CNFs Ti mesh CE exhibit an excellent power conversion efficiency (PCE) of 9.02% which is higher than that of benchmark Platinum (Pt) CE (7.47%) and pure CNFs CE (7.48%), showing an outstanding electrochemical performance. Interestingly, the CNFs CE exhibits similar PCE with Pt CE, which is mainly owing to the application of Ti mesh substrate. These results show that the Bi2MoO6/CNFs Ti mesh CE can be a promising low-cost-effective replaceable CE for DSSCs.