Well-defined side-chain ferrocene-containing polymers have been synthesized by post-modification of well-defined polyacrylonitrile (PAN). PAN prepared by Cu(0)-mediated single-electron transfer living radical polymerization was further modified using sodium azide and ammonium chloride (NH4Cl) to yield polymeric materials with vinyltetrazole units. Side-chain ferrocene-containing polymer was prepared by vinyltetrazole units and hydroxymethylferrocene after Mitsunobu reaction. FTIR, H-1 NMR, UV-Vis spectroscopy and thermogravimetric analysis were used to identify the structure of the target product. After linked the ferrocene unit, the final polymer showed typical redox property with a more negative redox potential (E-1/2).