Membrane distillation (MD) is the thermally driven water separation process based on the vapor pressure difference across the membrane. In order to increase the water recovery of the conventional RO process, the additional MD-PRO pocess was suggested. In this study, the syntheric RO brine was used as a feed solution of the MD process. Due to the high salinity of the RO brine, the MD membrane could be fouled by the scalants. In order to mitigate the scaling on the MD membrane surface, the pre-treatment process using the column filled by natural zeolite was applied. The roughing filter was installed between the pre-treatment process and MD system in order to prevent possible particulate fouling by the debries of the natural zeolite. Moreover, in order to enhance the CEC of the natural zeolite, the NaCl soaking was conducted. The flux and electronic conductivity were monitored under given experimental conditions. And the membrane morphology and the chemical compositions were analyzed by using the SEM-EDX.