Abstract: A new crown ether substituted polysiloxane, propyloxydibenzo-14-crown-4polysiloxane (PSO-DB-14C4) was synthesized and used as stationary phase for capillary column gas chromatography. The crown ether side-chair polysiloxane is a new gas chromatographic stationary phase, suitable for the separation of isomeric hydroxycompounds. The column is easily coated with this material possessing high efficiency and good thermal stability. A capillary column 30 m long was coated with this stationary phase and used for the separation of isomers of cresol and dimethylphenol. The chromatographic characteristics, including column efficiency, polarity, and selectivity were studied.