Electrostatic spinning (electrospinning) is a useful technique for producing ultrafine fibers with largespecific surface areas and porous structures. Polyvinylidene fluoride (PVDF) is a chemically stable material with extraordinary properties. In this research, PVDF fiber membranes were produced directly on papersurfaces by electrospinning to protect brittle paper relics from environmental damage. Tensile strengthand elongation tests for paper with and without the deposited PVDF membranes show that the PVDFfiber membranes can effectively protect paper under an externally applied force under both ambient andaging conditions. Water, insects, dust and mould can be isolated by the compact fiber structure whilecommon gases can pass through freely to maintain a favorable environment for the paper relics.