DBSA doped polypyrrole was prepared by In-situ chemical oxidative polymerization method. The reaction temperature was 0 to 20 °C. Different weight percentages of PSS (40 wt.%, 60 wt.% and 80 wt.%) were mechanically blended with a pestle in an agate mortar for 25 minutes by solid state mixing. The investigation of the blend focused on the optical, structural and morphological properties. SEM micrographs indicated that PSS was homogeneously distributed within DBSA doped PPy. FT-IR study confirmed the doped and blended dopants in the composite structure. UV-study revealed the π → π* transition in benzenoid rings of DBSA and presence of PSS. The semi-crystalline nature of the composites improved with increasing the weight percentage of PSS.