A method comprising a two-step alkali/acid treatment of poly (vinylidene fluoride) (PVDF) polymer is developed for the fabrication of flat-sheet PVDF membranes functionalized with labile hydroxyl groups. This method involves the application of a short-duration modification in alkali medium (5% KOH). Extensive characterizations were performed on the prepared membranes. Modification of the polymer altered the crystallinity of the PVDF from a mixture of both α and β phases to a predominant β phase. Lower work of adhesion of the modified membrane indicated the formation of a more hydrophobic and wetting-resistant membrane surface. Centrifugation of the polymer dope after the modification had a pronounced impact on the properties of the resultant membranes. This protocol could be utilized in fine-tuning the properties of PVDF membranes for various target-specific applications such as membrane distillation. This method can also be used in functionalizing PVDF membranes further by exploiting the labile –OH group present on the membrane surface.