Superhydrophobic membrane for the application in membrane distillation was generated by creating a hierarchical structure with multilevel roughness via depositing TiO2 nanoparticles on microporous PVDF membranes by means of a low temperature hydrothermal (LTH) process. The TiO2 coated membranes were then fluorosilanized using a low surface energy material H, 1H, 2H, 2H-perfluorododecyltrichlorosilane. A variety of techniques such as capillary flow porometry, TEM, SEM, XPS, KI test, liquid entry pressure (LEP) measurement and contact angle goniometry were applied to explore the effects of surface modification on the surface chemistry, structure and performance of the membranes. The anti-fouling performance of virgin and modified membranes were examined in a direct contact membrane distillation (DCMD) process using sodium chloride and humic acid solution as a model feed. Results showed that the modification was mechanically and thermally robust and photoactive. The liquid entry pressure (LEP) and water contact angle were increased from 120 kPa and 125 degrees to 190 kPa and 166 degrees, respectively. The fluorosilanization of TiO2 nanocomposite PVDF membranes did not compromise the mean pore size. It was also appeared that the TiO2 coating not only contributes in engineering the hierarchical structure but also provides sites (OH functional groups) for the hydrolyzed silane coupling agent to be anchored forming a robust uniform water repellent film. The filtration results also showed that the pure water flux of the modified membrane was lower than that of the virgin membrane particularly at higher temperatures. However, the sodium chloride DCMD test showed that the permeate conductivity of the virgin membrane was increased sharply whereas it was not changed for the modified membrane over the period of the experiment. A 20 h fouling DCMD experiment with humic acid did not show a reduction in flux for virgin and modified membranes. However, a substantial reduction in flux was observed with the addition of 3.775 mM CaCl2 into the solution due to the formation of complexes with humic acid and consequent particles coagulation and precipitation on the membrane surface. Although both virgin and modified membranes showed similar fouling behaviors, a significantly higher flux recovery was found for modified membrane compared to the virgin membrane. (c) 2012 Elsevier B.V. All rights reserved.