Inorganic/organic composite counter electrode comprised of CuI nanoparticles dispersed in PEDOT:PSS used for dye sensitized solar cells (DSSC). Various weight percentages of CuI (2, 5, 10, 15 and 20 wt %) were used to prepare different composite films. Performances of DSSCs with CuI/PEDOT:PSS with various contents of CuI were investigated. After the optimization of composition the composite film CuI (10 wt. %)/ PEDOT:PSS, a power conversion efficiency (PCE) of 4.60 % was achieved for the DSSC using TPA-CN1-R2 metal free dye as sensitizer, which is found to be higher than that of a DSSC with a Pt counter electrode (4.37 %) and PEDOT:PSS (3.00 %). The electrochemical impedance spectroscopy (EIS) and cyclic voltammetry measurements revealed that the composite counter electrode exhibited better catalytic activity, improved reduction rate of tri-iodide, than pristine PEDOT:PSS counter electrode. The homogeneous nature of the CuI/PEDOT:PSS composite film, uniform distribution CuI nanoparticles in its polymer matrix, and large electrochemical surface area of composite film are seen to be the factors for the better photovoltaic performance for DSSC.