In this work, we have fabricated a kind of N-doped hierarchal carbon fiber web by electrospinning hollow mesoporous carbon spheres (HMCSs) into fibrous structure. The as-synthesized carbon fiber web with novel mulberry-like morphology, thus denoted as MC-FW, possesses micro/meso/macroporous porosity, large surface area, high conductivity and multi-level structure, which are highly desired for supercapacitor electrode materials. The electrochemical measurements demonstrate that the designed MC-FW shows high capacitance (298.6 F g(-1)), favorable capacitance retention (71.0%) and long cycle life (97.3% capacitance retention after 5000 cycles). Notably, the capacitance of 298.6 F g(-1) for MC-FW is higher than the capacitance reported so far for many hollow carbon spheres and carbon fibers, which may contribute to the synergistic effect between the merits of HMCSs (e.g. micro/meso/macroporous hierarchal structure, large surface area, high pore volume) and advantages of 1D carbon fiber (e.g. large aspect ratio and high conductivity). It is believed that this distinctive carbon fiber web may show promising prospects as advanced energy storage materials and catalyst. (C) 2017 Elsevier Inc. All rights reserved.