Novel photoluminescence and optical investigation of one pot synthesized poly( vinyl acetate)/polyindole composites using chromium chloride as an oxidant. The prepared composite has been studied for optical parameters i.e. refractive index, extinction coefficient, optical conductivity, optical energy band gap and dielectric constants (real/imaginary) using UV-vis spectrum obtained. The most significant result of present study reflects that the 50 wt% samples have highest value of photoluminescence intensity and optical conductivity and also, have least optical energy band gap value. It was found to be 2.7699 eV. (C) 2015 Elsevier B.V. All rights reserved.