We report the preparation of hierarchically structured fullerene C70 cubes (HFC) composed of mesoporous C70 nanorods with crystalline pore walls. Highly crystalline cubic shape C70 crystals (FC) were grown at a liquid–liquid interface formed between tert-butyl alcohol and C70 solution in mesitylene. HFCs were then prepared by washing with isopropanol of the FC at 25 °C. The growth directions and diameters of C70 nanorods could be controlled by varying washing conditions. HFCs perform as an excellent sensing system for vapor-phase aromatic solvents due to their easy diffusion through the mesoporous architecture and strong π–π interactions with the sp2 carbon-rich pore walls. Moreover, HFCs offer an enhanced electrochemically active surface area resulting in an energy storage capacity 1 order of magnitude greater than pristine C70 and fullerene C70 cubes not containing mesoporous nanorods.