Cellulose triacetate (CTA) nanofiber nonwoven mats were continuously electrospun by using mixed solvent of DMSO/chloroform system. The size and morphology of CTA nanofibers were investigated. It was found that CTA fibers with diameters in the range of 98 nm–1.81 μm were obtained from 8 wt % CTA solutions in 1 : 1, 3 : 2, 2 : 1, 3 : 1, 5 : 1 and 7 : 1 (v/v) DMSO/chloroform. The average diameter of CTA nanofiber was decreased and size distribution was narrowed with increasing the DMSO content in the mixed solvent. Smooth and uniform nanofibers with mean diameters of about 260 nm could be obtained from a solution of CTA in the binary system DMSO/chloroform 5 : 1(v/v) at a polymer concentration of 8 wt %. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40373.