Macro-mesoporous carbon materials and hollow core/mesoporous shell (HCMS) carbon spheres have been prepared through an aqueous route with monodisperse silica spheres as hard template and F127 as soft template. By tuning reaction conditions and the ratio of SiO2/F127, ordered macro-mesoporous carbon materials, disordered macro-mesoporous carbon materials and HCMS carbon spheres were fabricated. All samples possess interconnected macropores and uniform mesopores with a narrow size distribution centred at 6-9 nm. The prepared HCMS carbon spheres show high specific surface area (972 m(2) g(-1)), large pore volume (1.27 cm(3) g(-1)) and thin shell thickness of 5 nm, which exhibit promising properties for supercapacitors with high capacitance due to its unique hollow structures.