Chitosan/poly(ε-caprolactone) (PCL) blend films in different mass ratios were prepared using the chitosan/PCL mixture solutions in 80 vol.-% acetic acid by spin coating. Their surface micromorphologies were assessed by atomic force microscopy (AFM). It was found that the micromorphology of chitosan/PCL blend films was in large extent related to the mass ratio of chitosan. 25 wt% chitosan/PCL blend film presented microphase separation. The protein adsorption of bovine serum albumin (BSA) onto chitosan/PCL blend films was investigated by using quartz crystal microbalance with dissipation monitoring (QCM-D) in real time. The results suggested that the amount of adsorbed BSA on the chitosan/PCL blend films decreased with the addition of chitosan, but the structure and viscoelastic properties of the adsorbed BSA layers were greatly affected by the surface micromorphology of chitosan/PCL blend films. BSA absorbed on the 25 wt% chitosan/PCL blend film with microphase separa- tion showed larger adsorption reversibility, and preferred to form a loose, dissipative layer in comparison with those on other chitosan/PCL blend films without microphase separation.