We report the improvement in the breakdown properties of electrowetting using a mixture of poly(acrylic acid) (PAA) polyelectrolyte and a surfactant (Tween 80, TW80). Onset of breakdown was initially determined via visual observation and further verified by investigating impedance phase shift. Breakdown characteristics of the large-molecule ionic solution were compared with those of conventional electrolytes (Na(2)SO(4)) that produce small molecules. Experiments with various conductivities and hydrophobic coatings on a thin silicon nitride dielectric layer (∼500 Å) showed that the breakdown voltage of the PAA-TW80 system was at least two times higher than that of the Na(2)SO(4)-TW80 system. Our results demonstrate that defects in the dielectric and hydrophobic layers are less vulnerable to larger ionic molecules.