Supported flat sheet nanocomposite polyvinylidenefluoride (PVDF) membranes embedded with hydrophilic TiO2, hydrophobic TiO2, or the combination of them were fabricated via phase inversion process. The membranes were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, atomic force spectroscopy, and the measurement of water contact angle and liquid entry pressure of water and subjected to tests on vacuum membrane distillation (VMD) performance. Addition of appropriate amounts of either hydrophilic or hydrophobic NPs was found to enhance VMD flux but hydrophilic NPs caused significant decrease of liquid entrance pressure of water (LEPw) while hydrophobic particles did not show significant impacts on LEPw, Addition of both hydrophilic and hydrophobic NPs demonstrated synergistic effects in terms of both enhanced flux and LEPw due to their different but complimentary effects on membrane structures. At feed temperature of 27.5 degrees C, the VMD pure water permeate flux of the composite membrane embedded with 5 wt% hydrophilic TiO2 NPs and 2 wt% of hydrophobic TiO2 NPs (total 7 wt% NPs) was 4.26 kg/m(2) h with a LEPw of 28 psi, while those of neat PVDF membrane, the membrane embedded with 7 wt% of hydrophilic NP, and the membrane with 7 wt % hydrophobic nanoparticles were 0.335, 3.57, and 1.25 kg/m(2) h, respectively, and the LEPw of these membranes were 51, 24 and 47 psi, respectively. It is noted that at 5 wt% addition, the flux of M-L5 (hydrophilic NPs) is 3 times higher than the M-B5 (hydrophobic NPs). Furthermore, by adding another 2 wt% of NPs, flux increment by M-L5-82 (hydrophobic NPs) is 3.5 times higher than M-L7 (hydrophilic NPs). Therefore, in both the effects combined, the highest flux was achieved by M-L5-B2 indicating synergistic effect of hydrophilic and hydrophobic NPs on the membrane flux. The salt rejection of above 99% could be maintained for 3 h by the membrane in which both hydrophilic and hydrophobic NPs were loaded. Numerical analyses of heat and mass transfer were also carried out to study the impact of hydrophilic and hydrophobic NPs on membrane characteristics.