Hierarchical nanostructured carbon with a hollow macroporous core of ca. 60 inn in diameter in combination with mesoporous shell of ca. 30 nm in thickness has been explored as counter electrode in metal-free organic dye-sensitized solar cell. Compared with other porous carbon counterparts such as activated carbon and ordered mesoporous carbon CMK-3 and Pt counter electrode, the superior structural characteristics including large specific surface area and mesoporous volume and particularly the unique hierarchical core/shell nanostructure along with 31) large interconnected interstitial volume guarantee fast mass transport in hollow macroporous core/mesoporous shell carbon (HCMSC), and enable HCMSC to have highly enhanced catalytic activity toward the reduction of I 3, and accordingly considerably improved photovoltaic performance. HCMSC exhibits a V-oc of 0.74 V. which is 20 mV higher than that (i.e., 0.72 V) of Pt. In addition, it also demonstrates a fill factor of 0.67 and an energy conversion efficiency of 7.56%, which are markedly higher than those or its carbon counterparts and comparable to that of Pt (i.e., fill factor of 0.70 and conversion efficiency of 7.79%). Furthermore, HCMSC possesses excellent chemical stability in the liquid electrolyte containing I-/I-3(-) redox couples, namely, alter 60 days of aging, ca. 87% of its initial efficiency is still achieved by the solar cell based on HCMSC counter electrode.