A new calixcrown polysiloxane gas stationary phase (M-C[4]C-5PSO) in which calixcrown monomers lie in the main chain of polysiloxane was first synthesized. The calixcrown polysiloxane exhibits high thermostability and good separation abilities for nitro, chloro- and methyl substituted benzene or phenol isomers. The application of M-C[4]C-5PSO and the separation mechanism will be further studied.