Polyvinyl alcohol (PVA) has excellent physical and chemical properties; however, its rigidity easily leads to brittleness and breakage during use. Additionally, due to intramolecular hydrogen bonding, the dense structure of the film limits its application. This research used a self-toughening approach by homogeneously blending PVA 0588 and PVA 0499 with different molecular weights to enhance the toughness of PVA and create a porous structure for broader application in membrane separation. Porous PVA membranes were then produced through mechanical stretching. Rheological testing, differential scanning calorimetry, and dynamic thermomechanical analysis confirmed that the blend system is partially compatible. Mechanical characterization revealed that adding PVA 0499 decreased the tensile modulus, strength, and bending modulus of the blended film but increased the elongation at break, reaching a maximum of 179 %. This result indicates that homogeneous blending effectively achieved PVA self-toughening. After this, the PVA blended membrane underwent mechanical stretching. Results showed that the stretched membrane developed a porous structure with a PVA 0588 content of 60 wt%, yielding a pure water flux of 70.3 L m−2 h−1 MPa−1 and a glucan rejection rate of 91.07 %. The molecular weight cut-off test demonstrated that the resulting porous membrane was suitable for water treatment, effectively filtering substances with a molecular weight of ≥70 kDa. The membrane also exhibited notable antifouling properties. The hydrophilicity and high roughness of the porous membrane facilitated the formation of additional hydrogen bonds between the membrane surface and water molecules, thereby reducing direct contact between pollutants and the membrane surface. This study provides preliminary theoretical and experimental insights into enhancing PVA toughness and expanding its applications in membrane separation. Furthermore, homogeneous blending opens new avenues for improving the mechanical performance of polymers.