The possibility of replacing traditional toxic solvents normally employed during the preparation of polymeric membranes with greener alternatives represents a great challenge for safeguarding the human health and protecting the environment. In this work, an improved and pleasant-smelling version of dimethylsulfoxide (DMSO), i.e., DMSO EVOL™, was used as "greener solvent" for the preparation of polyethersulfone (PES) microfiltration (MF) membranes using a combination of non-solvent and vapor-induced (NIPS and VIPS, respectively) phase separation technique for the first time. The effect of two different additives polyvinylpyrrolidone (PVP) and poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (Pluronic®) together with polyethylene glycol (PEG) on membrane properties and performances has been also evaluated. The membranes were characterized in terms of morphology, mechanical resistance, pore size, and water permeability. The obtained results show that DMSO EVOL™ is able to replace 1-methyl-2-pyrrolidone (NMP), which is a more toxic solvent normally used for the preparation of PES membranes. Furthermore, it was possible to tune the produced membranes in the range of MF (0.1-0.6 μm).