Polyvinylidene fluoride (PVDF) was blended with multi-walled carbon nanotubes (MWCNTs) and MWCNTs/SiO2 nano-additives to fabricate nanocomposite vacuum membrane distillation (VMD) membranes for desalination. The effects of MWCNTs and MWCNTs/SiO2 integrated additives on the morphology and performance of the PVDF membrane were studied. When only MWCNTs were used, 2 wt% loading of MWCNTs to PVDF had the maximum effect on the improvement of VMD flux, due primarily to the enlargement and elongation of the finger-like pores. Then, one of three different SiO2 nanoparticles (NPs) (hydrophobic, superhydrophobic and hydrophilic) was further added to the membrane that already contained 2 wt% of MWCNTs. When the amount of SiO2 NPs was relatively low, VIVID flux increased as a result of the synergistic effects between the two filler components, i.e. one is the increase of overall porosity by MWCNTs and the other is the growth of the macrovoids by SiO2 NPs. But among those two, the effect of MWCNTs was more dominant. Compared with the pristine PVDF membrane and the nanocomposite PVDF membrane with a single filler of MWCNTs, respectively, the flux increase by the addition of SiO2 was 292% and 55%. On the other hand, when a relatively large amount of SiO2 NPs was added, the effect of SiO2 NPs started to dominate. Especially, the asymmetric structure of the membrane disappeared, leading to low mechanical strength. All fabricated membranes exhibited great desalination potential with salt rejection as high as > 99.97%.