Fabrication of mesoporeous core-shell and hollow spheres with ordered mesostructure and tunable large pore size are highly desirable for fundamental research and practical applications. A direct triblock-copolymer-templating coating approach has been provided for synthesis of carbon sphere@mesoporous silica core-shell (CS@SBA-15) and hollow structures in an acidic medium at room temperature. These CS@SBA-15 core-shell structures possess large mesopores (6.3 – 8.4 nm), high surface areas (318.1 – 438.4 m2/g) and pore volumes (0.31 – 0.36 cm3/g). The corresponding hollow mesoporous silica spheres (HMSS) with controllable mesopores (6.0 – 8.2 nm), high surface areas (239.9 – 326.5 m2/g) and pore volumes (0.37 – 0.62 cm3/g) can be obtained after removal of the carbon sphere cores through calcination at 700 oC in air. The current research results provide an effective methodology for synthesis of other mesoporous silica core-shell structures with large pore size and multilayer core-shell even nanorattle structures.