In the present paper nano polymer composite of CuI/PVA blended with PEDOT: PSS has been prepared by growing CuI nano particles inside aqueous solution of PVA . The XRD characterization illustrated the growth of CuI nano-crystals of 22-33 nm size . The optical absorption showed direct transition with energy band gap equal to 1.2 eV and 1.3 eV for colloidal and thin solid films respectively . The PL investigation illustrates a reduction photoluminescence . The frequency dependence of conductivity suggests hopping conduction where the bulk conductivity is thermally activated with an activation energy in the range ( 0.07 – 0.46 ) eV . The cyclic voltammetry technique has been used to determine the position of both HOMO and LUMO levels and subsequently the chemical band gap which decreases from 1.72 to 1.3 eV with increasing PEDOT:PSS concentration .The results are interpreted according to energy confinement enhancement by plasmon-exciton interaction .