Cellulose triacetate (CTA) hollow fiber membrane used to separate methanol/methyl tert-butyl ether (MTBE) by pervaporation (PV) has been prepared from CTA hollow fiber reverse osmosis (RO) membrane for desalination of brackish water with high salinity. Acetone was selected as a modification agent of CTA membrane. PV performance depended on the solvent concentration, the treatment time and modification temperature of CTA RO hollow fiber membrane soaked in the aqueous acetone. The results show that CTA hollow fiber membrane modified with the solvent has a superior performance both the separation factor and the permeate flux in the PV experiment conditions.