Synthesis and characterization of poly(thiophene)s with pendant vinylene ferrocene (Fc) or cyanovinylene ferrocene units are described. Charge-transfer (CT) effects between the Fc groups and the conjugated polymer backbone have been demonstrated by the substantial photoluminescence (PL) quenching and spectroelectrochemistry. J-V studies on p/n bilayer devices (ITO/polymer/perylene imide (PV)/Ag) show significant photoconductance improvement when Fc concentration reached similar to40 mol % where short-circuit current density, J(sc), was increased 70% as compared to a similar ITO/P3BT/PV/Ag device.