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