A new β-ketoenamine-linked chiral covalent organic framework(COF), namely TfpMth COF, was prepared by the reaction of 1,3,5-triformylphloroglucinol(Tfp) with (S)-2,5-bis(2-methylbutoxy)terephthalohydrazide(Mth). The obtained TfpMth COF powder was characterized by various techniques such as powder X-ray diffraction analysis, Fourier transform infrared spectrometer(FTIR), thermogravimetric analysis(TGA), nitrogen adsorption-desorption measurement and so on, indicating its virtue of good crystallinity, high porosity, and excellent thermostability. Thus, we used TfpMth COF as a new stationary phase to prepare the TfpMth COF-bound capillary column by an in situ growth method. A series of linear and branched alkanes and alcohols, as well as mixtures of benzene and cyclohexane, ethylbenzene and styrene can be separated using the TfpMth-bound capillary column. This result provides a new idea for the application of β-ketoenamine-linked COF in chromatographic separation, and also gives a reference for the study of novel gas chromatographic stationary phases. © 2020, Higher Education Press. All right reserved.