Conductive polymer blends of polypyrrole (PPy) and poly(ethylene oxide) (PEO) were obtained in the form of films and fibers, respectively by solvent casting and electrospinning. Different amounts of PPy were introduced in the blends in order to study the effect of the conductive polymer on the properties of the final material and in particular to elucidate the influence of the different morphology on conductivity. The structure and morphology of PPy/PEO blends were characterized by wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to understand the influence of different PPy content on thermal behavior and stability, electrospun fibrous mats were examined by scanning electron microscopy (SEM). The conductivity of the films and fibrous mats was measured and correlation with morphology was highlighted.