Hierarchical nanostructured hollow core/mesopore shell carbon (HN-HCMSC) represents an innovative concept in electrochemical hydrogen storage. This work deals with physical characteristics and electrochemical hydrogen storage behavior of the HN-HCMSCs, produced by a replica technique using solid core/mesopore shell (SCMS) silica as template. HN-HCMSCs with various core sizes and/or shell thicknesses have been fabricated through the independent control of the core sizes and/or shell thicknesses of the SCMS silica templates. The superb structural characteristics of the HN-HCMSCs including large specific surface area and micropore volume, and particularly well-developed three-dimensionally interconnected hierarchical nanostructure (hollow macroporous core in combination with meso-/microporous shell), provide them with great potential for electrochemical hydrogen storage. A discharge capacity up to 586 mAh/g, corresponding to 2.17 wt % hydrogen uptake, has been demonstrated in 6 M KOH for the HN-HCMSC with a core size of 180 nm and a shell thickness of 40 nm at a discharge rate of 25 mA/g. Furthermore, the HN-HCMSC also possesses excellent cycling capacity retainability and rate capability.