Hybrid porous membranes with unique gradually open microchannels, which is comprised of polyvinylidene fluoride (PVDF) as skeletons and functional hyperbranched poly(ether amine) (hPEA) as coverage surface, are formed via a combined crystallization and diffusion approach. The cross‐sectional tortuous pores with fully well‐arranged, opened, and interconnected microchannels are generated that are directed by synergistic effect of the nucleation/crystallization of dimethylsulfoxide (DMSO) solvent, demixing/phase separation of polymers for both the loss of solvent in liquid phase and the reduced solubility of polymer at lower temperature, and exchanging effect between DMSO and water molecules. The introduction of functional amphipathic hPEA polymer chains effectively improves the hydrophilicity of pure PVDF with water permeation increased for 3.2 times, and contact angle decreases for about four times, and endowing the hPEA@PVDF hybrid membranes with high sensitive recognition and separation of phenols and anilines both in static and filtration processes. Moreover, the hybrid hPEA@PVDF membranes are easily regenerated and retained to their original states during adsorption–regeneration tests. This indicates that the hybrid membranes will be used in separation of toxic components that are carcinogenic, mutagenic, and difficult to biodegrade or direct aerobic digestion in nature via a one‐pot filtration process in water treatments.