Abstract Four cyclodextrin (CD) phenyl carbamates were synthesized by introducing phenyl carbamate groups in different substitution positions of β-CD. The chromatographic properties of these CD phenyl carbamates as capillary gas chromatography (CGC) stationary phases were investigated. The results showed that most of these CD phenyl carbamates were moderate polar stationary phases with their polarities being related to not only phenyl carbamates groups but also other functional groups substituted in CDs. The polarities, coating properties and the properties of substituted functional groups of these cyclodextrin phenyl carbamates affected their separation properties greatly. It was found that these new CD phenyl carbamates as stationary phases had separation ability to disubstituted benzene positional isomers.