This review is an account of the development, utilization, and characterization of polymeric pseudostationary phases (PSPs) for EKC since the previous review in this series in 2007. Improvements in performance by means of new polymeric phases and modifications to previously reported materials are described. The use of EKC and spectroscopic studies to characterize the interactions between polymeric PSPs and analytes is discussed. The application of polymeric PSPs for techniques or approaches to which they provide particular advantages is reviewed. Chief among these is the application of polymeric PSPs for the combination of EKC with MS detection.