Porous membranes with uniform nanostructures and selective adsorption can realize molecular filtration with high flux and have gained great attention because of their wide application in water treatment and industrial separation. Herein, a novel hyperbranched poly(ether amine)@poly(vinylidene fluoride) (hPEA@PVDF) porous membrane with oriented nanostructures and selective adsorption of guest molecules was fabricated by applying the combined crystallization and diffusion method for the functionalization of the PVDF membrane. The resulting hPEA@PVDF porous membranes were fully characterized by scanning electron microscopy and X-ray photoelectron spectra. The results indicated that the hPEA@PVDF membrane exhibited oriented open channel structure and high water flux up to 2116 L m(-2) h(-1), in which the PVDF skeleton was covered by the amphiphilic hPEA layer. The adsorption behavior of hPEA@PVDF porous membranes to 12 hydrophilic dyes including batch adsorption and molecular filtration was systematically investigated. The results revealed that the hPEA@PVDF membrane possessed high adsorption capacity toward erythrosin B (577 mu mol g(-1)) and eosin B (511 mu mol g(-1)), while low adsorption capacity toward calcein (76 mu mol g(-1)) and methylene blue (hardly adsorbed), indicating the selective adsorption behavior toward dyes in aqueous solution. On the basis of this selective property, the hPEA@PVDF could be used to separate the dye mixtures very efficiently through molecular filtration. In addition, the separation efficiency remained 100% after five adsorption-desorption cycles, indicating that it had great potential in practical applications.