Pb(II)-imprinted chitosan/TiO2 hybrid film (LIHF) was synthesized through a two-step process. The selectivity of LIHF was studied via competitive adsorption experiment. The LIHF shows higher selectivity to Pb (II) ion than Cu (II) and Zn (II) ions. X-ray photoelectron spectroscopy(XPS) was used to characterize the as-obtained samples. XPS results showed that the nitrogen atom and the Pb (II) were concerned for coordination. The evidences for the imprinting process and the recognition of Pb (II) with LIHF were provided.