In this article, poly(vinylidene fluoride) (PVDF) hollow fiber membrane and acrylic acid (AA) were co-irradiated by high-energy electron beam to introduce hydrophilic carboxylic groups on the membrane surface. Thermal capability, mechanical performance, pore size, and permeation property were investigated to determine the stability of the membrane pore structure before and after irradiation polymerization. The decomposition temperature, melting point, glass transition temperature, and breaking force of the PVDF-g-AA membrane increased slightly because of irradiation grafting polymerization. After 15 months of storage, the pore size distribution of the PVDF-g-AA membrane became smaller and more dispersive. The pure water flux and the rejection to bovine serum albumin of the PVDF-g-AA membrane increased significantly with the increase in hydrophilicity and decrease in pore size. The results indicated that the structure and properties of the PVDF hollow fiber membrane were stable after high-energy electron beam irradiation grafting polymerization, even after 15 months of storage. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41165.