Hierarchically porous carbon materials with high surface areas are promising candidates for energy storage and conversion. Herein, the facile synthesis of hierarchically porous carbons through the calcination of metal-organic framework (MOF)/chitosan composites is reported. The effects of the chitosan (CS) additive on the pore structure of the resultant carbons are discussed. The corresponding MOF/chitosan precursors could be readily converted into hierarchically porous carbons (NPC-V, V=1, 2, 4, and 6) with much higher ratios of meso-/macropore volume to micropore volume (Vmeso-macro /Vmicro ). The derived carbon NPC-2 with the high ratio of Vmeso-macro /Vmicro =1.47 demonstrates a high specific surface area of 2375 m2  g-1 , and a high pore volume of 2.49 cm3  g-1 , as well as a high graphitization degree, in comparison to its counterpart (NPC) without chitosan addition. These excellent features are favorable for rapid ion diffusion/transport, endowing NPC-2 with enhanced electrochemical behavior as supercapacitor electrodes in a symmetric electrode system, corresponding to a high specific capacitance of 199.9 F g-1 in the aqueous electrolyte and good rate capability. Good cycling stability is also observed after 10 000 cycles.