Hexavalent chromium (Cr (VI)) is a highly toxic pollutant which is harmful to marine organisms as well as humanity. Removing Cr (VI) from water is a hot-spot in environmental remediation. In this work, a novel kind of composite nanofibers membrane (thermal plastic elastomer ester (TPEE) A100H) was first proposed by a simple method, based on a hybrid strategy composed of electrospinning and hydrothermal method. The obtained nanofibrous membrane was turned out to be a petaloid structure, which can enlarge the specific surface area of electrospun fibers. Furthermore, the Cr (VI) removal experiments suggested that the obtained nanofibrous membrane showed a high and fast efficiency, a stable recyclable property for the Cr (VI) removal. Therefore, such a novel nanofibrous membrane can be potentially widely used in Cr (VI) removal.