The efficient capture of uranium from wastewater is crucial for environmental remediation and the sustainable development of nuclear energy, yet it poses considerable challenges. In this study, amphiphilic ionic covalent organic framework intercalated into graphene oxide (GO) nanosheets functionalized with polyethyleneimine (PEI) were used to construct hybrid membranes with ultrafast uranium adsorption. These hybrid membranes achieved equilibrium in just 10 min and the adsorption capacity was as high as 358.8 mg g−1 at pH = 6. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) analyses revealed that the strong interaction between sulfonic acid groups and uranyl ions was the primary reason for the high adsorption capacity and selectivity. The extended transition state and natural orbitals for chemical valence (ETS–NOCV) analysis revealed that the interaction between the 7 s and 5f orbitals of uranyl and the 2p orbitals of S and O in the sulfonate was the primary reason for the strong interaction between the sulfonate and the uranyl ion. This research presents an effective method for the rapid extraction of uranium from wastewater.