The NaA/PTFE composite membranes were synthesized on polytetrafluoroethylene (PTFE) film by hydrothermal secondary growth (HSG) method and scratching (ST) method. The structure and morphology were characterized by XRD and SEM. The pervaporation(PV) performance of NaA/PTFE composite membranes were evaluated with dimethylformamide (DMF)/water mixtures. The XRD results showed that NaA/PTFE composite membranes kept the zeolite crystal feature of A type. The substrate, PTFE and zeolite were firmly combined together by the SEM photos. The results of PV showed that the flux and the separation factor of NaA/PTFE composite membrane prepared by HSG method with 4 crystallization times were 0.54 kg/m2 h and 23, respectively. The flux of NaA/PTFE composite membrane prepared by ST method was much larger than that of NaA/PTFE composite membrane prepared by HSG method, but separation factor was lower.