Cocontinuous cellulose acetate (CA)/polyurethane (PU) composite nanofibers were obtained through electrospinning of partially miscible CA and PU in 2:1 N,N-dimethylacetamide (DMAc)/acetone mixture solvent. Their structures, mechanical, and thermal properties were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The structures and morphologies of the nanofibers were affected by com ponent ratio in the binary mixtures. PU component not only facilitated the electrospinning of CA at CA concentration down to 12 wt%, but reinforced the tensile strength of CA/PU nanofibrous mats, while semirigid component CA in the composite nanofibers could greatly improve the rigidity and dimensional stability of CA/PU nanofibrous mats. In a series of nanofibrous mats with varied CA/PU composition ratios, CA/PU 20/80 showed excellent tensile strength and Young's modulus. The residual product after selective removal of any one of the components in CA/PU composite nanofibers by washing with proper solvent maintained the fiber structure but greatly reduced the fiber size, suggesting CA/PU composite fibers showed a cocontinuous nanofiber structure due to phase separation in the spinning solution and in the course of electrospinning.