A capillary gas chromatographic column with Nafion film as stationary phase was prepared via a verified dynamic coating procedure.The separation performance of the Nafion film coated capillary column was studied with linear alkanes,linear alcohol,pinene isomer and aromatic isomer,and its morphology was analyzed by SEM.Results showed that the column could offer effective separations for linear alkanes,terpene isomer as well as aromatic positional isomer.Effect of temperature on separation of terpene isomer and aromatic positional isomer was investigated,which was used to elucidate that the separation process for aromatic positional isomer was controlled by both entropy and enthalpy,but the separation process for terpene isomer was controlled only by enthalpy.