The stationary phases including the nonpolar and polar stationary phases in microscale separations have been greatly developed. This review describes the recent progress of the polar stationary phases (PSPs) with the focus on their preparation and the interesting applications in the field of CEC and capillary liquid chromatography (CLC) covering the literatures from the middle of 2006 to the middle of 2008. The PSPs described herein were summarized into three types as open-tubular, particle-packed and monolithic stationary phases for either CEC or CLC, and the separation mechanisms are of hydrophilic interaction, chiral selection, ion-exchange and/or electrostatic interaction, etc. After overviewing the literatures published in the last 2 years, the research efforts on PSPs for CEC and CLC have been remaining in the fabrication of open-tubular and monolithic capillary columns; whereas, the research endeavor of PSPs on particulate-packed format seemed to decline most likely due to the commercial availability of various packing particles for CEC and CLC.