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Organic solvent nanofiltration (OSN) membranes are always troubled by the “trade-off” effect between solvent flux and solute rejection. Hence, a rapid, convenient, and effective way to synthesize novel β-cyclodextrin-enhanced zeolite imidazole framework-8 (β-CD@ZIF-8) nanoparticles was first proposed and the nanoparticles were doped into both selective layer and poly(m-phenylene isophthalamide) support for fabricating thin-film nanocomposite membranes. Transmission/scanning electron microscopy images and X-ray photoelectron spectroscopy results demonstrate the successful synthesis of β-CD@ZIF-8. Atomic force microscopy images illustrate the more rougher surface compared to the pristine membrane, while the pure acetone flux reached 62.3 ± 2.3 L m–2 h–1, and Rose Bengal rejection achieved 96.6 ± 1.8 and 94.5 ± 0.5% in methanol (MeOH) and tetrahydrofuran at 0.6 MPa, respectively, when the dosage was 0.05% (w/v). The molecular weight cutoff around 574 Da of PPA2505 containing β-CD@ZIF-8 in both support and selective layers shows the optimum properties and outstanding OSN performances in erythromycin concentration and purification in MeOH and butyl acetate. Additionally, polyimide nanofiber and the formed net structure may offer a potential way to fabricate “ultrathin” film in the OSN industry.