Spherical C@PSt microspheres with average size around 2 μm were successfully prepared using high-speed homogenization-assisted suspension polymerization of styrene in the presence of carbon black modified by oleic acid. The effects of initiator varieties and initiators concentration on the fractional conversion were investigated. Compared with BPO, AIBN has higher efficiency to initiate the polymerization. LPSA, SEM and OM results showed the prepared microspheres had spherical morphology with the carbon black in the core and PSt in the shell. About 10 weight percentages of carbon black were encapsulated in the complex microspheres proved by TGA results.