A ship in bottle nanocomposite was fabricated as a novel adsorbent for lanthanides by immobilizing a lanthanide-sensitive polymer into mesocellular siliceous foam (MCF). The MCF was used as a novel carrier for immobilization of the polymer, and the polymer was synthesized via in situ ring-opening polymerization of 2-methyl-2-oxazoline (MOL) and divinylbenzene (DVB) in the presence of MCFs. The substantially physically modified MCF-based composite exhibited superior adsorptivity and selectivity to lanthanides due to its exceptional properties, which was employed for lanthanide adsorption from aqueous solution by a facile solid–liquid separation procedure. The adsorption of lanthanides by the composite was systematically studied including adsorption parameter investigation and adsorption mechanism evaluation. The adsorption isotherms and kinetics were also investigated and proved to follow the Langmuir model and the pseudo-second-order model. The adsorption thermodynamics study indicated that the adsorption process was thermodynamically favorable, endothermic and spontaneous. The prepared inorganic–organic hybrid composite has superior selectivity and specificity to lanthanides, which can be used for lanthanide enrichment and separation of lanthanides from actinides.