A novel film based on zeoliticimidazolate framework-4 (ZIF-4) as a separator is prepared by hydrothermal method and a stable electrode-supported separator is synthesized by blade-coating technology. The ZIF-4 separator with the thicknesses of about 60 μm is coated on Li[Ni1/3Co1/3Mn1/3]O2 electrode with a slurry of ZIF-4, PVDF and amount of N-methyl-2-pyrrolidone (NMP). It is found that the ZIF-4 separator has good thermal stability and cycle performance than conventional polypropylene (PP) separator. And it has larger liquid electrolyte uptake, higher retention, higher ionic conductivity and lower interfacial resistance. The C-rate performance of ZIF-4 separator is superior than PP separator, and it enhances the safety of lithium-ions battery. Therefore, the ZIF-4 separator is a promising material to improve stability and safety of lithium-ions battery.