The intertwined TiN nanofibers with mesopores structure were fabricated by an electrospinning method followed by a nitridation reaction. TiN nanofibers counter electrodes (CEs) based DSC delivered dramatically enhanced photovoltaic performances, compared with particulate TiN CE. The nanofibers intertwined to form a 3D conducting pathway facilitating the electron transfer, while the tunable surface areas and mesoporous provided abundant catalytic active sites and reduced the diffusion impedance of triiodide ions, leading to the high J(sc) and FF for DSCs. Based on these advantages, the highest conversion efficiency of devices employing TiN nanofibers CEs yielded 7.08%, which was higher than that of device with Pt CE (6.84%). Therefore, the facile procedure, low cost and excellent photovoltaic properties endow the intertwined TiN nanofibers to be a promising alternative CE for future large-scale application of DSCs.