An iron cyclopentadienyl complex of a conducting polymer, poly (n-hexylphenylene) (abbreviated as PHP), was prepared by a reaction of PHP with ferrocene, Al and AlCl 3 followed by an anion exchange using NH 4 PF 6 . Cyclic voltammetry of the complex thus formed with a formula, {(C 6 H 3 C 6 H 1 3 ) 1 . 6 [ (η 6 -C 6 H 3 C 6 H 1 3 )Fe( η 5 -C 5 H 5 )] PF 6 } n (abbreviated as PHP-[FeCp]PF 6 , Cp = η 5 -cyclopentadienyl),has indicated that it is reduced with a moderate chemical reversibility in Bu 4 NBF 4 -THF at E 0 = -1.7 V versus Ag/Ag + . Spectroelectrochemical measurements have suggested that the chemical reaction of the reduced form is a coupling reaction of phenylene rings coordinated to iron, resulting in a formation of insoluble thin network polymer film on the electrode surface. Photoluminescence of PHP is modified in intensity and maximum emission wavelength by coordinating the FeCp moiety.