In this study, double-shelled C/SiO 2 hollow spheres with an outer hydrophilic silica shell and an inner hydrophobic carbon shell were initially prepared by activating a solid silica layer of the C/SiO 2 aerosol particles. The low-cost preparation technique that can be easily scaled-up includes a rapid aerosol process and a subsequent dissolution-regrowth process. A large surface area (226.3 m 2 /g), high pore volume (0.51 cm 3 /g), and high mechanical stability of the spheres benefit their high adsorption capacities for methylene blue (MB) and metal ions. The novel spheres show high adsorption capacity of 171.2 mg/g for the MB, which is higher than that for the single-shelled silica hollow spheres (150.0 mg/g). The adsorption efficiency of the hollow spheres remains higher than 95% after regeneration for five times. The saturation adsorption values of Pb 2+ and Ag + ions on the hollow spheres are 216.5 and 283.1 mg/g, respectively, which are higher than 189.8 and 213.4 mg/g on the single-shelled SiO 2 spheres. Moreover, the adsorption capacity of the fifth recycled spheres for the Pb 2+ and Ag + ions reaches as high as ~180 and ~245 mg/g, respectively. These results reveal that the outer porous silica layer with a ζ-potential of −37.4 mV has the main contribution to the excellent adsorption performance of the spheres. In addition to the contribution to the adsorption capacity of the double-shelled hollow spheres, the inner carbon layer plays a crucial role in supporting the outer silica shell and in improving the adsorption efficiency, mechanical stability, and recycling property of the hollow spheres.