Cellulose acetate@chitosan modified montmorillonite composite nanofibers were fabricated by electrospinning and solution intercalation (CA@CS-MMT). And the adsorption properties of CA@CS-MMT nanofibers for Cr (Ⅲ) in wastewater were studied. Firstly, the CS-MMT composite was prepared by intercalation modification of MMT with CS, and the interlayer spacing of modified CS-MMT was significantly increased from 1.2450 nm to 2.2198 nm. Then CA@CS-MMT composite nanofibers were prepared by solution blending electrospinning. The structure and properties of the composite nanofibers were studied by SEM, FTIR, XRD and TGA etc. The results showed that the average diameter of nanofibers decreased with the increase of CS-MMT content. And the thermal stability and wettability of nanofibers were improved. When the content of CS-MMT is 2 wt%, the lamellar structure of CS-MMT is assembled with CA to form a continuous structure in the nanofiber. The adsorption capacity of the composite nanofibers was 144.93 mg/g when pH was 5.5 ? 0.1 at 25 ℃. The adsorption process was in accordance with Langmuir isothermal adsorption and pseudo second order kinetics. The adsorption capacity was still 95.0 mg/g after three times of desorption.