Various hydrophilic poly(ethylene-co-vinyl alcohol) (EVOH) were used herein to precisely control the structure and hydrodynamic properties of polysulfone (PSF) membranes. Particularly, to prepare pristine PSF and PSF/EVOH blends with increasing vinyl alcohol (VOH: 73%, 68%, 56%), the non-solvent-induced phase separation (NIPS) technique was used. Polyethylene glycol was used as a compatibilizer and as a porogen in N,N-dimethylacetamide. Rheological and ultrasonic separation kinetic measurements were also carried out to develop an ultrafiltration membrane mechanism. The extracted membrane properties and filtration capabilities were systematically compared to the proposed mechanism. Accordingly, the addition of EVOH led to an increase in the rheology of the dopes. The resulting membranes exhibited a microporous structure, while the finger-like structures became more evident with increasing VOH content. The PSF/EVOH behavior was changed from immediate to delayed segregation due to a change in the hydrodynamic kinetics. Interestingly, the PSF/EVOH32 membranes showed high hydrophilicity and achieved a pure water permeability of 264 L·m^–2·h^–1·bar^–1, which was higher than that of pure PSF membranes (171 L·m^–2·h^–1·bar^–1). In addition, PSF/EVOH32 rejected bovine serum albumin at a high rate (> 90%) and achieved a significant restoration of permeability. Finally, from the thermodynamic and hydrodynamic results, valuable insights into the selection of hydrophilic copolymers were provided to tailor the membrane structure while improving both the permeability and antifouling performance.