The development of high-performance polymer membranes has sparked a lot of attention in recent years. Polymer blending is a potential method of modification. A limitation, however, is the compatibility of blends at the molecular level. In this investigation, polyethersulfone/polyetherimide hollow fiber membranes were prepared by the solution blending method. Compatibility, hydrogen bonding, crystallinity, microstructure, hydrophilicity, mechanical properties, and transmissibility of blended membranes were also characterized. The compatibility and hydrogen bonding action of the two components were confirmed by DSC, FTIR, XPS, and XRD. The structure exhibits a C−H···O interaction motif with the sulfone group acting as a hydrogen bond acceptor from a methyl C−H donor. The π–π stacking between the two polymers arranged molecules more orderly, resulting in enhanced intermolecular interactions. Compared to polyethersulfone hollow fiber membranes, the hydrophilic, mechanical properties, and rejection rate of the blended membranes are more effectively enhanced. Self-assembly of the host polymer with a polymer capable of forming hydrogen bonds to construct controllable blends is a crucial and proven method.