This work provides an easy and versatile strategy to manufacture novel polyvinylidenefluoride (PVDF) membranes by solution casting and phase separation techniques displaying tailored physicochemical and microstructural features depending on the opportune combination of functionalization by blending chemical additives (multiwalled carbon nanotubes, MWCNTs) and manufacturing procedure. The systematic study of the effect of (i) polymer concentration, (ii) use of pore forming additives (LiCl), and (iii) type and concentration of MWCNTs, on the PVDF crystalline composition and membrane microstructure, highlights the strong relationships of these parameters with the wettability, fouling and transport attributes of the formed membranes. The results provide the key to discriminate membrane preparation conditions favoring hydrophilic, low fouling, and highly selective PVDF–MWCNTs membranes, for water-treatment applications in pressure-driven membrane operations, from conditions favoring the formation of hydrophobic and waterproof membranes, to be used in the membrane contactors field. Also, they open exciting perspectives for a more effective development of PVDF-based nanostructured membranes for advanced separations based on a comprehensive investigation and understanding of material's properties.