Three new kinds of poly (crown ether)siloxane and three low-molecular-weight crown ethers have been used as stationary phases of open-tubular gas chromatographic column. The fused silica capillary columns coated with the poly (crown ether ) siloxanes possess high efficiency, high thermostability and good selectivity. These columns are suitable for separation of alcohols and phenols, for example, 9 isomers of cresol and dimethylphenol can be separated successfully on the PSO-DB-14C4 column.