Three new kinds of poly (crown ether)siloxane as capillary gas chromatographic stationary phases are presented. The behavior of the capillary columns coated with these polymers was studied)and experimental result shows that these columns exhibited an excellent property. They possess a high efficiency, a good thermostability and a nice selectivity.therefore these columns are suitable for the separation of a variety of isomers separating difficultly on the other conventional stationary phases.