Tamisolve^® NxG, a well-known non-toxic solvent, was used for poly(vinylidene fluoride) (PVDF) membranes preparation via a non-solvent-induced phase separation (NIPS) procedure with water as a coagulation bath. Preliminary investigations, related to the study of the physical/chemical properties of the solvent, the solubility parameters, the gel transition temperature and the viscosity of the polymer–solvent system, confirmed the power of the solvent to solubilize PVDF polymer for membranes preparation. The role of polyvinylpyrrolidone (PVP) and/or poly(ethylene glycol) (PEG), as pore former agents in the dope solution, was studied along with different polymer concentrations (10 wt%, 15 wt% and 18 wt%). The produced membranes were then characterized in terms of morphology, thickness, porosity, contact angle, atomic force microscopy (AFM) and infrared spectroscopy (ATR-FTIR). Pore size measurements, pore size distribution and water permeability (PWP) tests placed the developed membranes in the ultrafiltration (UF) and microfiltration (MF) range. Finally, PVDF membrane performances were investigated in terms of rejection (%) and permeability recovery ratio (PRR) using methylene blue (MB) in water solution to assess their potential application in separation and purification processes.