β-Cyclodextrins/polyacrylonitrile/copper nanorods (β-CDs/PAN/CuNRs) composite fibers were fabricated by two steps including the preparation for the β-CDs/PAN composite fibers by electrospining, and the preparation of the β-CDs/PAN/CuNRs composite fibers by adsorption and reduction. The β-CDs/PAN/CuNRs composite fibers were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy respectively. The results indicated that the CuNRs were not only successfully synthesized on the surface of composite fibers but also the CuNRs were distributed without aggregation on the composite fibers. Furthermore, microorganism Escherichia coli had been used to check the antibacterial efficacy of the β-CDs/PAN/CuNRs composite fibers. Subsequently, antibacterial tests have indicated that the composite fibers have good bactericidal effects. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41011.