Cyclotriveratrylene (CTV) is reported here for the first time as stationary phase for capillary gas chromatographic (GC) separations. CTV stationary phase showed weak polarity comparable to the conventional 5% phenyl polysiloxane stationary phase but exhibited different retention behaviours and higher resolution for some of the indicated analytes. Most importantly, CTV stationary phase exhibited preferential selectivity for halogenated compounds, positional and geometrical isomers. Effect of column temperature on retention and thermal stability of CTV column were also investigated. Moreover, CTV capillary column showed good repeatability in terms of run-to-run, day-to-day and column-to-column. The unique physicochemical features and efficient separation ability for analytes of close properties show the potential of CTV as a new-type stationary phase in GC as well as separation science.