The design and fabrication of polymer microspheres with structural complexity in Pickering emulsion systems is a pioneering topic in recent years. Herein we report a synthesis of structured and molecularly imprinted multicore rattle-type microspheres through a facile method based on the Pickering emulsion polymerization using silica nanoparticles as the only stabilizer. The void inside the sphere was induced by the polymerization-driven phase separation approach tailoring by the interface interaction. However, the imprinting template of bisphenol A (BPA) is found to serve also as the heterogeneous nuclei, whose superimposition on the polymerization induced phase separation creates the opportunities for the formation of the multicores encapsulated in the shell. A simple adjustment on the composition of the oil phase enabled the evolution of sphere internal structures from single void to multicores. Specifically, the reversibly incorporated BPA on the polymer spheres can be removed by extraction with the molecular information left and immobilized by crosslinking as the imprinted sites. The imprinted spheres can be used to selectively rebind BPA, which was comprehensively evaluated by a batch of rebinding experiments. The rattle-like microspheres recognized BPA molecules from their analogues and ef7fectively removed them from the matrix with accelerated adsorption kinetics, which shows potential applications in the environmental or analytic fields where the removal or separation of BPA as an endocrine-disrupting chemical is in high demand.