Membrane pervaporation provides an effective approach for production of desalinated water and treatments of salted water. The water permeation fluxes through the membranes could be the key issue for practical systems. In this work, a surface engineering through introduction of lotus-leaf biomimicked structures and chemical deprotonation has been performed on poly(vinyl alcohol) membrane surfaces. The increased surface area and hydrophilicity of the membranes significantly enhance water dissolution into the membrane, so as to bring a 2.8 times of water permeation flux to the membrane. In addition to a high thickness-normalized water flux of 386 kg-μm h−1 m−2, the surface-engineered PVA membrane also exhibit ability for desalination on high salinity water (15 wt% NaCl(aq)). The surface-engineering method could be integrated with other approaches for membrane modification to exhibit synergistic effect on enhancements of membrane separation performance.