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. The optical absorption showed direct transition with an energy band gap equals to 1.18 eV and 1.3 eV for colloidal and thin solid films respectively. The PL investigation illustrates a quenching with increasing PEDDOT:PSS concentration. The results are interpreted according to energy confinement enhanced by plasmon-exciton interaction of CuI-PVA/PEDOT:PSS core-shell. The frequency dependence of conductivity suggested hopping conduction where the bulk conductivity is thermally activated with an activation energy in the range varies from 0.07 to 0.46 eV by increasing PEDOT:PSS concentration. The cyclic voltammetry measurements have been performed to ascertain the position of both HOMO and LUMO levels which illustrated a movement of HOMO level toward vacuum level, with a decrease in the chemical band gap from 1.72 to 1.3 eV with increasing PEDOT:PSS concentration. (C) 2014 Elsevier GmbH. All rights reserved.