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In this work, Rhodiasolv® PolarClean was employed as a more sustainable solvent for the preparation of poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) flat sheet membranes via phase inversion technique by coupling vapour induced phase separation (VIPS) and non-solvent induced phase separation (NIPS) processes. Preliminary calculations based on Hansen solubility parameters well predicted the solubilization of the polymer in the selected solvent. The effect of exposure time on humidity and the influence of polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP) and sulfonated polyether sulfone (S-PES) on membrane properties and performance, were evaluated. Three different coagulation bath compositions were also explored. The obtained membranes, prepared using a more sustainable approach, were compared with those produced with the traditional toxic solvent N-methyl-2-pyrrolidone (NMP) and characterised in terms of morphology, porosity, wettability, pore size, surface roughness and mechanical resistance. The potential influence of the new solvent on the crystallinity of PVDF-HFP-based membranes was also evaluated by infrared spectroscopy. The adjustment of the parameters investigated allowed tuning of the membrane pore size in the microfiltration (MF) and ultrafiltration (UF) range resulting in membranes with various morphologies. From the water permeability and rejection tests, performed with methylene blue dye, the prepared membranes showed their potentiality to be used in MF and UF applications.