Effect of electroactive ferrocene on the optical and electrochemical properties of polythiophenes were examined. Thus the ferrocene unit were introduced into polythiophenes by Grignard metathesis (GRIM) method to produce ferrocene substituted polythiophenes (PThFc). These polymers were characterized by GPC, NMR, UV-Vis absorption spectrum, and cyclic voltammogram (CV). The PThFc showed lower redox potential and reversible electrochemical redox state due to the ferrocenyl functional group, as determined by the CV. The absorption maxima of PThFc was 556 nm in the film state with a broad absorption band covering from 350 nm to 650 nm. Fluorescence quenching efficiency of PL for the PThFc containing films was determined as > 90%. The short-circuit current densities (Jsc) for the cell containing PThFc was highly dependent on the thermal annealing process, indicating that the photovoltaic properties could be optimized by the control of polymer structure. (PThFc).