Cyclodextrin–polymer composite electrospun nanofibers were developed for micropollutant (MP) removal from water. The fibers were fabricated by electrospinning of mixed poly(ether sulfone) (PES) and β-cyclodextrin (CD) solutions under optimal conditions. The composite fibers were compared with bare PES nanofibers prepared by the same method. Scanning electron microscopy revealed that CD did not alter the fiber morphology, while the fiber capacity for MP uptake was enhanced by CD through the formation of inclusion complexes. The availability of CD on the fibers was confirmed by the emergence of visible luminescence due to the inclusion of a quantum cluster, Au₂₅SBB₁₈ (SBB = 4-(tert-butyl)benzylmercaptan in thiolate form), in the cavities of CD exposed on fiber surfaces. The steroid hormone estradiol (E2) (100 ng/L) and pesticide chlorpyrifos (CP) (5 mg/L) were used as model pollutants in batch experiments designed to measure uptake potential. The nanofibers interact strongly with the model pollutants because of their high surface area and surface affinity. Increases of 20% in E2 uptake and 80% in CP uptake compared with bare PES nanofibers were observed. This behavior indicates promising applications of CD-containing materials for MP removal in water treatment and membrane technology.