Hydrophobic polydimethylsiloxane - polytetrafluoroethylene (PDMS-PTFE) flat-sheet membranes for pervaporation (PV) of chloroform from aqueous solution were successfully fabricated by solution casting method. The structures and the performance of the membranes was characterized by X-ray diffraction (XRD), scanning electron microscope combined with energy dispersive X-ray spectroscopy (SEM-EDXS), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and the tests of contact angle and mechanical properties. The adding of PTFE particles (<4 μm) in the PDMS matrix enhanced the crystallinity, hydrophobicity, mechanical strength and thermal stability of the membranes. The examinations showed that the PTFE filled PDMS membranes exhibited striking advantages in flux and separation factor as compared with unfilled PDMS membranes. All the filled PDMS membranes with different PTFE content showed excellent PV properties for the separation of chloroform from water. When the content of the PTFE additive in PDMS composite membrane was 30 wt%, membrane performance was the best at feed temperature 50 ℃ and permeate-side vacuum 0.101MPa. For the 30% PTFE-PDMS membrane, with the increase of the feed temperature from 30 to 60 oC, the total, water and chloroform fluxes as well as the separation factor increased, the apparent activation energy (ΔEa) of total, chloroform and water were 21.08, 66.65 and 11.49 KJ/mol, respectively with an increase of chloroform concentration in the feed from 50 to 950 ppm, total, water and chloroform fluxes increased but the separation factor decreased.