Abstract: The chromatographic behavior of 36 kinds of aliphatic alcohols were studied with OV-1 and Superox 0.6 cross-linking capillary columns. Results showed both columns with good resolution for the alcohols. The OV-1 column could separate the alcoholic components except the 3-pentanol/2-pentanol pair, it revealed a higher column efficiency and temperature limit, the separation was following close to the boiling point of the components. The efficiency and temperature limit of the Supemx 0.6 column was lower than OV-1. Owing to the separation of the Superox 0.6 is based on the H-bonding interaction, so that it revealed its own unique selectivity and different retention characteristics, the retention time to primary alcohols were longer, but, to tertiary alcohols were obviously reduced due to its steric hindrance.