Novel surfactant systems that allow the formation of polymerizable microemulsions are required for the synthesis of ultrafine polymer latices. The work reported here extends the ability to formulate new microemulsion ''recipes'' by means of a new approach: the geometry and polarity of a given surfactant can be adjusted by electrostatic coupling with an appropriate organic counterion, e.g., the generation of a very bulky hydrophobic head group. It is demonstrated that counterion variation of classical surfactants leads to a significant improvement of classical microemulsions.