The fabrication of mesoporous core-shell and hollow spheres with ordered mesostructures and tunable large pore sizes is highly desirable for fundamental research and practical applications. A direct triblock-copolymer-templating coating approach has been provided for the 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-1) and large pore volumes (0.31-0.36 cm3 g-1). The corresponding hollow mesoporous silica spheres (HMSS) with controllable mesopores (6.0-8.2 nm), high surface areas (239.9-326.5 m2 g-1) and pore volumes (0.37-0.62 cm3 g-1) can be obtained after the removal of the carbon sphere cores through calcination at 700 degrees C in air. The current research results provide an effective methodology for the synthesis of other mesoporous silica core-shell structures with large pore sizes and multilayer core-shells, and even nanorattle structures.