A new modified polysiloxane, perylene-containing polysiloxane (PCP), was successfully synthesized by amine-terminated polysiloxane (ATP) and 3,4,9,10-perylene tetracarboxylic dianhydride. The synthesized compound was characterized by Fourier transform infrared spectroscopy (FT-IR) and (1)H nuclear magnetic resonance ((1)H NMR). The thermal analysis of the PCP indicates that the modified polysiloxane has outstanding thermal stability. The PCP also possesses good fluorescence property. Due to the appearance of lone-pair electrons and pi bond in PCP, it could be self-assembled on iron surface and thus used in the corrosion protection area. The PCP films were characterized by EIS (electrochemical impedance spectroscopy) and SEM (scanning electron microscopy). These results indicate that the films modified by PCP could protect the iron from corrosion efficiently. (C) 2011 Elsevier B. V. All rights reserved.