Monodispersed poly(styrene-co-N-dimethylaminoethyl methacrylate) [P(St-DMAEMA)] composite microspheres were prepared by employing a Shirasu Porous Glass (SPG) emulsification technique. A mixture of monomer, hexadecane (HD), and initiator N,N'-azobis(2, 4-dimethylvaleronitrile) (ADVN) was used as a dispersed phase and an aqueous phase containing stabilizer [poly(vinyl pyrrolidone) (PVP) or poly(vinyl alcohol)(PVA)], sodium lauryl sulfate (SLS), and water-soluble inhibitor [hydroquinone (HQ), diaminophenylene (DAP), or sodium nitrite (NaNO2)], was used as a continuous phase. The dispersed phase was permeated through the uniform pores of SPG membrane into the continuous phase by a gas pressure to form the uniform droplets. Then, the droplets were polymerized at 70 degreesC. The effects of inhibitor, stabilizer, ADVN, and DMAEMA on the secondary nucleation, DMAEMA fraction in the polymer, conversion, and morphologies of the particles were investigated. It was found that the secondary nucleation was prevented effectively in the presence of HQ or DAP when PVP was used as the stabilizer. The secondary particle was observed when ADVN amount was raised to 0.3 g (/18 g monomer); however, no secondary nucleation occurred even by increasing DMAEMA fraction to 10 wt %. This result implied that the diffusion of ADVN into the aqueous phase was a main factor responsible to the secondary nucleation more than that of DMAEMA. The hollow particles were obtained when NaNO2 was used, while one-hole particles formed in the other cases. By adding crosslinking agent, the hole disappeared and the monomer conversion was improved.