The polymer dynamics at the water interface play a crucial role in the manifestation of biorelated functions. One of the strategies for this is to form inclusion complexes of polymer chains with cyclic compounds. However, such an idea has been limited to bulk materials so far. Here we propose a preparation pathway for a polyrotaxane structure composed of poly(ethylene oxide) (PEO) and a-cyclodextrin (CD) at the outermost surface of a glassy poly(methyl methacrylate) film on the basis of the combination of a click reaction and the Langmuir-Blodgett method. The chain motion of PEO at the water interface could be regulated by threading of CD molecules on PEO and thereby the biological responses such as protein adsorption and platelet adhesion altered depending on the extent of complexation.