Ultrafine fibers with diameters ranging from 50 to 300 nm were prepared from DNA/single-walled carbon nanotubes (SWNTs)/poly(ethylene oxide) blended dispersion. Well-defined electrospun fibers were obtained by good control of key dispersion properties related to electrospinning, such as ionic conductivity, surface tension, and viscosity. Raman spectroscopy confirmed the presence of SWNT in the resulting fibers, indicating good interaction between DNA and SWNT. The resulting fibers also exhibited electroactive behavior and could be used as an immobilization matrix for a glucose oxidase enzyme biosensor. The sensor response was linear up to 20 mM glucose with a sensitivity of 2.4 mA cm-2 M-1.