Nearly monodispersed concentric hollow nanospheres with a mesoporous silica shell and anatase titania inner core were synthesized by the combination of sol-gel reaction and distillation-precipitation polymerization. The well-defined. mesoporous concentric hollow nanospheres, comprising two nanostructured functional inorganics, can be used for confined catalytic reactions. The direct synthesis procedures can be readily extended to preparation of the concentric hollow nanospheres with multiple cores, or other functional concentric hollow nanospheres having different core-shell compositions.