Nanofibers composed of cellulose acetate (CA) and montmorillonite (MMT) were prepared by electrospinning method. MMT was first dispersed in water and mixed with an acetic acid solution of CA. The viscosity and conductivity of the CA/MMT solutions with different MMT contents were measured to compare with those of the CA solution. The CA/MMT solutions were electrospun to fabricate the CA/MMT composite nanofibers. The morphology, thermal stability, and crystalline and mechanical properties of the composite nanofibers were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and tensile test. The average diameters of the CA/MMT composite nanofibers obtained by electrospinning 18 wt% CA/MMT solutions in a mixed acetic acid/water (75/25, w/w) solvent ranged from 150 similar to 350 nm. The nanofiber diameter decreased with increasing MMT content. TEM indicated the coexistence of CA nanofibers. The CA/MMT composite nanofibers showed improved tensile strength compared to the CA nanofiber due to the physical protective barriers of the silicate clay layers. MMT could be incorporated into the CA nanofibers resulting in about 400% improvement in tensile strength for the CA sample containing 5 wt% MMT.