Abstract As a common used and hardly emulsified amorphous thermoplastic, the bisphenol-A polycarbonates were used as the polymer candidate to form a novel monodispersed sub-micrometer mesoporous polymer–silica spheres with full interpenetrating structure. The synthesis procedure was based on a modified sol–gel approach in which the polycarbonate was plasticized in advanced by the surfactant of polymer emulsion. The mesoporous spheres possess a perfect uniform particle size and the polymer–silica spheres are held together by permanent entanglement in three dimensions. The defined crystallization of the polycarbonate was occurred when it was entrapped in the silica laminated matrix due to the plasticizing effect of the surfactant, and directly affected the thermal stability of the mesoporous spheres. The specific surface areas and pore diameters of mesoporous sphere were affected by the mass content and crystallization behavior of the polycarbonate. The p-phenylenediamine was used as adsorbate to investigate the cationic organics adsorption ability of the mesoporous spheres. The results shown that the polycarbonate-silica possess a well adsorption capacity for p-phenylenediamine by virtue of two kinds of hydrogen bond, and the maximum adsorption capacity was nearly 7.5 times larger than that of the hollow mesoporous silica.