Several types of synthetic ionic polymers have been employed as pseudostationary phases in electrokinetic chromatography. The polymers have been shown to have some significant advantages and different chemical selectivity relative to conventional surfactant micelles. Polymeric phases are effective for the separation and analysis of hydrophobic and chiral compounds, and may be useful for the application of mass spectrometric detection. Additionally, the polymeric phases often demonstrate unique selectivity relative to micellar phases, and can be designed and synthesized to provide desired selectivity. This review covers efforts to develop and characterize the performance, characteristics, and selectivity of synthetic polymeric pseudostationary phases since their introduction in 1992. Some ideas for the future development of polymeric pseudostationary phases and the role they may play in electrokinetic separations are presented.