The encapsulation of stearic acid coated nanometer CaCO3 by a polystyrene (PS) network via emulsion polymerization is described, where γ-methacryloxypropyltrimethoxysilane (MPS) was used as an efficient crosslinker. The important factors such as the type and amount of surfactant and initiator and the content of CaCO3 are investigated as well as the role of MPS. It has been shown that little PS was extractable with only 0.6 wt% of MPS (relative to styrene). The cationic surfactant cetyl trimethylammonium bromide (CTAB) proved more effective than the anionic surfactant sodium dodecyl sulfonate (SDS). The yield rises, particles become smaller and size distribution broadens with increased amount of CTAB. It is also found that either 2,2′-azobis(isobutyronitrile) (AIBN) or ammonium persulfate (APS) is suitable for attaining high monomer conversion. With increased amount of CaCO3, the encapsulation ratio can be varied from 17.9 to 3.6, while monomer conversion and yield decrease slightly. FT-IR spectra of the products after extraction indicate tight encapsulation between PS and CaCO3, and TEM photographs of composite particles with well-defined core-shell structure give direct evidence of encapsulation.