The x-polyethylene glycol diacrylate (x-PEGDA) coated polyetherimide/polyvinylidene fluoride (PEI/PVdF) membranes are obtained by the facile combination of dip-coating and free radical polymerization of PEGDA on the electrospun PEI/PVdF fiber membranes. Successful cross-linking of PEGDA increases the average fibers diameter from 553 to 817 nm and reduces the packing density, which not only increases the tensile strength of x-PEGDA coated PEI/PVdF membranes, but also decreases the average pore diameter. Besides, the x-PEGDA coated PEI/PVdF membranes are endowed with good wettability, high electrolyte uptake, high ionic conductivity and improved electrochemical stability window because of the good affinity of PEI and PEGDA with liquid electrolyte. Benefiting from the synergetic effect of PEI and PVdF, the x-PEGDA coated PEI/PVdF membranes exhibit excellent thermal stability and nonflammability, which are beneficial for enhancing the safety of lithium ion batteries. More importantly, the x-PEGDA coated PEI/PVdF membranes based Li/LiFePO4 cell exhibits comparable cycling stability with capacity retention of 95.9% after 70 cycles and better rate capability compared with the Celgard membrane based cell. The results clearly demonstrate that the x-PEGDA coated PEI/PVdF membranes are the promising separator candidate with improved wettability and safety for next-generation lithium ion batteries.