In this paper, the possibilities offered by anionic polymerization were exploited to engineer well-defined PS-b-PEO2 gemini-type dispersants that were fitted with terminal styrenic groups. Two routes were explored to obtain this novel generation of surfactants whose thorough characterization indicated that they exhibit the expected molecular structure. These reactive block copolymers have been subsequently used as surfactants in the emulsion polymerization of styrene to stabilize the colloidal particles formed. The kinetics of polymerization in the presence of such reactive surfactants were shown to differ from the case involving PS-b-PEO linear macromonomers as surfactants.