One-dimensional hierarchical hollow nanostructures composed of NiO nanosheets are successfully synthesized through a facile carbon nanofiber directed solution method followed by a simple thermal annealing treatment. With the advantages of high electro-active surface area, carbon nanofiber supported robust structure and short ion and electron transport pathways, the hierarchical hybrid nanostructures deliver largely enhanced capacitance with excellent cycling stability when evaluated as electrode materials for supercapacitors. More specifically, a high capacitance of 642 F g(-1) is achieved when the charge-discharge current density is 3 A g(-1) and the total capacitance loss is only 5.6% after 1000 cycles.