Tuning the cohesive and swelling forces in porous membranes by post-synthesis solvent-treatment was already proven to be a successful way to increase the membrane selectivity in aqueous redox flow battery application without sacrificing too much permeability of the membranes. This method was now extended to non-aqueous applications and the mechanism behind the tuning of the pore sizes upon solvent-treatment was studied in more detail. Porous polyvinylidene fluoride (PVDF) and polysulfone (PSF) membranes were thus prepared via phase inversion and subsequently treated with different solvents followed by the evaporation of this solvent to adjust the structural porosities of these asymmetric membranes and better understand the underlying mechanism. For this purpose, water and acetonitrile permeances were determined before and after the solvent-treatment and these permeances were linked to the (solvent)-(membrane polymer) Hansen solubility parameters. The membrane density changes were characterized by positron annihilation lifetime spectroscopy (PALS). It was proven that the pore adjustment that was created by the solvent-treatment was reversible when the membrane was later on applied in a feed solution with high affinity for the membrane polymer.