Two new stationary phases, cone bis(undecenyloxy)-p-t-butyl calix [4]crown-5 polysiloxanes (PSO-C-c[4]c-5) and partial cone 5,11,17,23-t-butyl-25,27-diethoxy-26,28-diundecenyl calix[4]arene polysiloxane (PSO-PC-c[4]E), are synthesized and used as stationary phases in capillary column gas chromatography. Their chromatographic characteristics, such as column efficiency, capacity factor, average polarity, operation temperature range, and peak asymmetry were measured. Their column efficiency is over 3000 plates m −1 , and their average polarities are between that of OV-1701 and SE-54. Their maximum allowable operating temperature is up to 310˚C. Then, 33 aromatic compounds and positional isomers were used to test the separation abilities of the two stationary phases. The results indicate that the synthetic calixarene stationary possess good separation ability for aromatic compounds and positional isomers. It is noticeable that the retention behavior of several positional isomers on the PSO-C-c[4]c-5 column are different from that on PSO-PC-c[4]E column. The separation mechanism is also discussed.