In this work, hydrophobic poly(vinylidene fluoride) membranes for potential membrane distillation applications, with pore sizes ranging from ~ 0.05 to ~ 0.30 μm, were prepared by employing triethyl phosphate (TEP) as a substitute to the hazardous, commonly used, toxic solvents. Membrane morphologies and properties were tailored based on the main parameters, such as the casting solution composition and the operational conditions, which affect the phase inversion process. Experimental results showed that exposure time to controlled humid air and temperature, as well as additive content in the dope solution, strongly influence the membrane formation. The use of TEP as an alternative solvent may contribute to the development of sustainable separation operations.